阅读说明：本技术 包含具有边缘改性和/或表面改性的粘土片晶的附聚的超吸收聚合物颗粒 (Super-absorbent polymer particles comprising the agglomeration with the clay platelet that edge is modified and/or surface is modified ) 是由 J.坎波斯 A.西蒙扬 于 2018-03-20 设计创作，主要内容包括：本发明提出了附聚的超吸收聚合物颗粒,并且所述附聚的超吸收聚合物颗粒通过包括以下步骤的方法获得：a)提供具有第一质量平均粒度<Sup>1</Sup>mAvPS的前体超吸收聚合物颗粒,以及b)将所述前体超吸收聚合物颗粒与包含下列物质的溶液混合：i)均匀分散于其中的粘土片晶,所述粘土片晶具有相对基层片晶表面和片晶边缘；ii)一种或多种表面改性化合物和/或边缘改性化合物；以及iii)可聚合单体和/或低聚物或iv)可交联聚合物,c)如果所述溶液包含可聚合单体和/或低聚物,则使所述混合溶液聚合,或者如果所述溶液包含可交联聚合物,则使所述混合溶液交联。所述附聚的超吸收聚合物颗粒具有大于所述第一质量平均粒度<Sup>1</Sup>mAvPS至少25％的第二质量平均粒度<Sup>2</Sup>mAvPS。(The invention proposes the super-absorbent polymer particles of agglomeration, and the super-absorbent polymer particles of the agglomeration are obtained by method comprising the following steps: a) providing has the first mass average particle size 1 The precursor super-absorbent polymer particles of mAvPS, and b) the precursor super-absorbent polymer particles are mixed with the solution comprising following substance: i) being dispersed in clay platelet therein, the clay platelet has opposite base's platelet surface and platelet edge；Ii) one or more surface modifying compounds and/or edge modified compound；And iii) polymerisable monomer and/or oligomer or iv) crosslinkable polymer, if c) solution includes polymerisable monomer and/or oligomer, then it polymerize the mixed solution, or if the solution includes crosslinkable polymer, is crosslinked the mixed solution.The super-absorbent polymer particles of the agglomeration, which have, is greater than the first mass average particle size 1 The second mass average particle size of mAvPS at least 25% 2 mAvPS。)

1. the super-absorbent polymer particles of agglomeration are obtained by method comprising the following steps:

A) providing has the first mass average particle size¹The precursor super-absorbent polymer particles of mAvPS, and

B) the precursor super-absorbent polymer particles are mixed with the solution comprising following substance:

I) it is dispersed in clay platelet therein, the clay platelet has opposite base's platelet surface and platelet edge；

Ii) one or more surface modifying compounds and/or edge modified compound；And

Iii) polymerisable monomer and/or oligomer；Or

Iv) crosslinkable polymer；

If c) solution includes polymerisable monomer and/or oligomer, it polymerize the mixed solution, or if described Solution includes crosslinkable polymer, then is crosslinked the mixed solution,

Wherein the super-absorbent polymer particles of the agglomeration, which have, is greater than the first mass average particle size¹MAvPS's at least 25% Second mass average particle size²mAvPS。

2. the super-absorbent polymer particles of agglomeration according to claim 1, wherein the polymerisable monomer and/or oligomer Polymerisable monomer and/or oligomer comprising acrylic acid or its salt or acrylate or derivatives thereof.

3. the super-absorbent polymer particles of agglomeration according to any one of the preceding claims, wherein the solution includes the The crosslinking agent of one type, the crosslinking agent of the first kind include acrylate or acrylamide group.

4. the super-absorbent polymer particles of agglomeration according to any one of the preceding claims, wherein the solution includes the The crosslinking agent of two types, the crosslinking agent of the Second Type be amide acetals, carbamate, polyalcohol such as glycol or polyol, Cyclic carbonate, double oxazolines, epoxides or glycidol ether.

5. the super-absorbent polymer particles of agglomeration according to any one of the preceding claims, wherein step c's) is laggard Row:

D) super-absorbent polymer particles of the dry agglomeration,

Wherein the second mass average particle size²MAvPS is measured after step d).

6. the super-absorbent polymer particles of agglomeration according to any one of the preceding claims, wherein step c's) is laggard Row:

D) super-absorbent polymer particles of the dry agglomeration,

E) super-absorbent polymer particles of the agglomeration are classified to obtain granularity lower limit,

Wherein the second mass average particle size²MAvPS is measured after step e).

7. the super-absorbent polymer particles of agglomeration according to any one of the preceding claims, wherein before step b) or Simultaneously the precursor super-absorbent polymer particles are carried out with step b) surface-crosslinked.

8. the super-absorbent polymer particles of agglomeration according to any one of the preceding claims, wherein the clay flake crystalline substance selects From kaolinite such as kaolin, illite such as glauconite, terre verte or the montmorillonite including hectorite, hectorite, saponite, leech Stone or their mixture.

9. the super-absorbent polymer particles of agglomeration according to any one of the preceding claims, wherein described one or more Edge modified compound is by one or more phosphorylated compounds, silanized compounds or fluorinated compound or their combination group At.

10. the super-absorbent polymer particles of agglomeration according to any one of the preceding claims, wherein described a kind of or more Kind surface modifying compound includes alkylation nitrogen part or alkoxylate nitrogen part, including straight chain, branching or cricoid amination Close object, ammonium compounds, it is preferable that one or more surface modifying compounds include to be selected from following part: straight chain or branch Change polyethyleneimine, hexamethylene diamine or ethylenediamine or any of these derivatives or their mixture.

11. the super-absorbent polymer particles of agglomeration according to any one of the preceding claims, wherein the agglomeration is super Absorbent polymer particles are surface-crosslinked.

12. the super-absorbent polymer particles of agglomeration according to any one of the preceding claims, wherein when the agglomeration It is described according to free swell rate (FSR) test method when super-absorbent polymer particles have the size lower than 850 μm The super-absorbent polymer particles of agglomeration have greater than 1.00g/g/s, preferably more than 1.05g/g/s, more preferably larger than The average swelling rate for reaching 20g/g of 1.10g/g/s.

13. the super-absorbent polymer particles of agglomeration according to any one of the preceding claims, wherein such as being tested according to CRC Method measurement, the super-absorbent polymer particles of the agglomeration with 18g/g to 40g/g, preferably 22g/g to 40g/g from Heart retention capacity (CRC) value.

14. a kind of absorbent article, it includes the super-absorbent polymers of agglomeration according to any one of the preceding claims Grain.

15. absorbent article according to claim 14, including absorbent cores, wherein the absorbent cores (28) include one or more A region (29), the region is substantially free of absorbing material.

Technical field

The present invention relates to by using with the clay platelet-shaped that edge is modified and/or surface is modified at agglomeration superabsorbent Pinching polymer beads, and it is related to the absorbent article of the super-absorbent polymer particles of the agglomeration comprising obtaining via context of methods.

Background technique

The purposes of super-absorbent polymer particles, the purposes especially in absorbent article are ripe for people in the art Know.Super-absorbent polymer particles usually shred relatively large super-absorbent polymer block by grinding or in other ways to make It is standby.However, the size of the particle obtained by such grinding or chopping cannot be fully controlled.Therefore, the super-absorbent polymerization of acquisition Composition granule usually has specified particle size distribution, thus there are relatively large-sized particle (such as 1000 μm or even more big) and its His particle is fairly small, and all such as less than 100 μm or even significant smaller, wherein most granularity is in the range to fall between It is interior.Particle is usually from known as " particulate ".

It is known in order to make the absorbent article comprising super-absorbent polymer particles show good absorption and receiving function, need To meet specific technical requirements by super-absorbent polymer particles.

Super-absorbent polymer particles are firstly the need of can quickly absorb liquid efflunent.In the prior art, superabsorbent pinching The infiltration rate of polymer beads passes through the free swell rate (FSR) of measurement particle generally to characterize.

Other than with high-selenium corn speed, what absorbent article was included is present in the super-absorbent polymer in absorbent cores Grain also needs permeable to liquid height.In the prior art, the permeability of super-absorbent polymer particles usually passes through measurement The UPM (urine permeability measurement) of grain is characterized.

The poor permeability of super-absorbent polymer particles can cause the infiltration of absorbent article due to gel blockage.Work as swelling Super-absorbent polymer particles blocking particles between void space when, gel blockage can occur in an absorbent core.In such feelings Under condition, liquid efflunent cannot or only slowly reach the lower layer of the super-absorbent polymer particles of setting in an absorbent core.Liquid flow Object is retained on the surface of absorbent cores and can be therefore from leakage from absorbent articles out.

To solve the problems, such as gel adhesion, super-absorbent polymer particles are commonly subjected to surface-crosslinked, therefore increase particle Deformation resistance when rigidity and swelling.

Although the surface-crosslinked permeability for helping to increase super-absorbent polymer particles, infiltrative increase is usually to subtract Small capacity is cost: since particle has compared with hard surface, so they are unobstructed unlike not surface-crosslinked particle Ground swelling.This tradeoff is more obvious for lesser superabsorbent polymer particles.

A kind of method for reducing fine grain quantity but need not abandoning them is to form the agglomeration of super-absorbent polymer particles Body.

The patent application US2010/0234531 of Evonik Stockhausen GmbH, which is disclosed, a kind of prepares the super of agglomeration The method of absorbent polymer particles.

Patent application WO2015/175620 discloses the super-absorbent polymer particles of agglomeration, by using with trivalent Or the multivalent salts agglomeration of higher chemical valence.

Although it have been described that forming a variety of methods of the super-absorbent polymer particles of agglomeration, but still need to prepare agglomeration Super-absorbent polymer particles improved method and the agglomeration needed to be improved super-absorbent polymer particles.

Summary of the invention

The invention discloses the super-absorbent polymer particles of agglomeration, the super-absorbent polymer particles of the agglomeration are by including The method of following steps obtains:

A) providing has the first mass average particle size¹The precursor super-absorbent polymer particles of mAvPS, and

B) precursor super-absorbent polymer particles are mixed with the solution comprising following substance:

I) it is dispersed in clay platelet therein, which has opposite base's platelet surface and platelet edge；

Ii) one or more surface modifying compounds and/or edge modified compound；And

Iii) polymerisable monomer and/or oligomer；Or

Iv) crosslinkable polymer,

If c) solution includes polymerisable monomer and/or oligomer, it polymerize the mixed solution, or if this is molten Liquid includes crosslinkable polymer, then is crosslinked the mixed solution.

The super-absorbent polymer particles of agglomeration, which have, is greater than the first mass average particle size¹The second matter of mAvPS at least 25% Measure average particle size²mAvPS。

First mass average particle size "¹MAvPS " is to be polymerize according to the precursor super-absorbent of screening test method as described herein The quality average particle size of composition granule.

Second mass average particle size "²MAvPS " is the superabsorbent pinching according to the agglomeration of screening test method as described herein The quality average particle size of polymer beads.

The invention further relates to a kind of absorbent article, which includes the agglomeration obtained via method described herein Super-absorbent polymer particles.

Super-absorbent polymer particles comprising the agglomeration with modified surface and/or the clay platelet at edge are shown well Performance characteristics.In particular, the super-absorbent polymer particles of agglomeration can have high osmosis, good absorptive capacity and high-selenium corn speed Degree.In fact, having the clay platelet of the modified surface and/or edge that are connected to precursor super-absorbent polymer particles to keep certain Power to increase the elongation at break of the super-absorbent polymer particles of agglomeration.Include the clay with modified surface and/or edge The super-absorbent polymer particles of the agglomeration of platelet therefore can better against deformation to avoid or reduce gel adhesion.

Further, since the hydrophily of the clay platelet with modified surface and/or edge, thus have modified surface and/ Or the clay platelet at edge can avoid the aggregation of clay platelet, this can be conducive to liquid diffusion.Therefore, the super-absorbent of resulting agglomeration Polymer beads can have good infiltration rate.

Detailed description of the invention

Fig. 1 is in the top view of the Exemplary absorbent articles of diaper form, and the diaper may include agglomeration of the invention Super-absorbent polymer particles, some of layers are partly removed.

Fig. 2 is the transverse sectional view of the diaper of Fig. 1.

Fig. 3 is in the top view of the Exemplary absorbent articles of diaper form, which may include the super of agglomeration of the invention Absorbent polymer particles, wherein one or more regions are substantially free of absorbing material.

Fig. 4 is the transverse sectional view of the product of Fig. 3.

Fig. 5 is the transverse sectional view in the product intercepted with Fig. 4 same point, and wherein channel is since diaper is loaded with stream Body and formed in core.

Fig. 6 is the partial cross-section side view for carrying out the suitable permeability measuring system of urine permeability measurement test Figure.

Fig. 7 is the cross-sectional side view for carrying out the piston/cylinder sub-assembly of urine permeability measurement test.

Fig. 8 is the top view of the piston head suitable for piston/cylinder sub-assembly shown in Fig. 7.

Fig. 9 is the cross-sectional side view of the piston/cylinder sub-assembly for the Fig. 7 being placed on the sintering pan for being swollen phase.

Figure 10 is the figure using the super-absorbent polymer particles of the agglomeration of the embodiment E1 of scanning electron microscope (SEM) Piece.

Specific embodiment

Term " absorbent article " refers to absorption and accommodates the device of body exudates, and more specifically refers to abutting or neighbour The body of nearly wearer is placed to absorb and accommodate the device for the various effluents being discharged from body.Absorbent article may include diaper (baby' diaper and the diaper for adult-incontinence), trousers, liner, feminine care absorbent articles such as sanitary napkin or panty liner Deng.Term " effluent " includes but is not limited to urine, blood, vaginal fluid, sweat and excrement.Preferred absorption of the invention Product is disposable absorbent article, more preferably disposable diaper and disposable pant.

" disposable " is used with its common meaning, refers to that the use of the finite number of time in different durations is (such as small In 20 times use, less than 10 times use, less than 5 times use, or less than 2 times use) after it is processed or abandon product.If The disposable absorbent article is diaper, trousers, sanitary napkin, menopad or the wet wipe for personal hygiene, then described primary Property absorbent article is generally intended to processed after a single use.

" diaper " and " trousers ", which refers to, generally to be worn by baby and incontinent patients around lower body, so as to around the waist of wearer With leg and the absorbent article particularly suitable for receiving and accommodating urine and excrement.In trousers, first lumbar region and second lumbar region Longitudinal edge is attached to each other with pre-formed waist opening and leg opening.By the way that the leg of wearer is protruded into leg opening and by trousers Absorbent article drawing wears trousers with wearer to the position near wearer's lower body.Any suitable method can be used in trousers Carry out preform, including but not limited to using the bonding of repeatable fastening and/or not reproducible fastening (for example, suture, welding, Adhesive, adhesive bonds, fastener etc.) each section of absorbent article is bonded together.Trousers can be along any of article periphery Position preform (for example, side fastening, Attacking Midfielder's fastening).In diaper, waist opening and leg opening are only logical in diaper It crosses and is just formed when being worn such as under type to wearer: making indulging for first lumbar region and second lumbar region with suitable fastening system It (releasedly) is attached to each other on bilateral to edge.

" absorbent cores " used herein, which refer to, to be arranged between the top flat of absorbent article and egative film, for absorbing and accommodating by inhaling Receive the structure of the received liquid of product.If in addition to the absorbent core, absorbent article further includes top flat and/or egative film, and/or is adopted Collecting system, then the absorbent cores do not include top flat, egative film and/or acquisition system.

" comprising " and "comprising" are open-ended terms, each the presence of specified such as one component described thereafter, but not Exclude the presence of other feature known in the art or disclosed herein such as element, step or component.These are based on verb The term of " comprising " should be understood to include the narrower terms " Consists of " for excluding any unspecified element, step or ingredient And by the scope limitation of element at specified material or the "consisting essentially of ..." of step, and element execution is not significantly affected Those of mode of its function.Any preferred or exemplary implementation scheme described below does not limit the scope of the claims, Unless clearly indicating such progress.Word " typically ", " usual ", " advantageously " etc. also limit element, are not intended to be limited to power The range that benefit requires, unless clearly indicating such progress.

Precursor super-absorbent polymer particles

" super-absorbent polymer " refers to following absorbing material, they are cross-linked polymeric materials, when use Centrifuge Retention Capacity (CRC) test method (EDANA method NWSP 241.0.R2) is come when measuring, the polymeric material can absorb at least 10 times it Own wt 0.9% aqueous saline solution.These polymer usually in granular form (" water-absorbing polymer particles " or " super-absorbent polymer particles ") use is to be flowable in the dry state.Term " particle " refer to granule, fiber, Thin slice, sphere, powder, thin plate and other shapes known to technical staff and form in super-absorbent polymer particles field.

The precursor super-absorbent polymer particles that can be used to form the super-absorbent polymer particles of agglomeration of the invention can have A variety of shapes.

Precursor super-absorbent polymer particles can be spherical super-absorbent polymer particles or ellipticity super-absorbent polymer particles Or irregular super-absorbent polymer particles or fibrous super-absorbent polymer particles, i.e., elongated needle-shaped super-absorbent polymer Grain.In the specific embodiment, precursor super-absorbent polymer particles fiber, which has, is less than about 1mm, generally less than about 500 μ M, and preferably less than 250 μm down toward 45 μm of small scale (i.e. the diameter of fiber).The length of fiber is preferably from about 3mm to about 100mm。

Preferably, the precursor super-absorbent polymer of super-absorbent polymer particles that are of the invention and being used to form agglomeration Grain is spherical particle.It is described according to the present invention and with fiber on the contrary, " spherical particle " has longest and a smallest dimension, and In the range of 1:5, intermediate value 1 will be equal to perfect spherical particle, and value 5 will be examined for the ratio between the longest of grain and smallest particles scale Consider and this spherical particle there are some deviations.

As according to measured by EDANA method WSP 220.2-05, precursor super-absorbent polymer particles of the invention can have There are 45 μm to 850 μm, preferably 45 μm to 500 μm, more preferably 45 μm to 300 μm, even more preferably less than 150 μm of grain Degree.

The precursor super-absorbent polymer particles that can be used in the present invention include that a variety of water that can absorb a large amount of fluids are insoluble Property but water-swellable polymer.Such polymer material is generally known in the art.

Preferred precursor super-absorbent polymer particles of the invention are made of poly- (methyl) acrylate copolymer.However, for example Absorbent polymeric material and polyacrylamide copolymer, the copolymerization of ethylene maleic acid acid anhydride based on starch granules also can be used Object, cross-linked carboxymethyl cellulose, polyvinyl alcohol copolymer, cross-linked polyethylene oxide and the starch-grafted of polyacrylonitrile are total to Polymers.

In general, precursor super-absorbent polymer particles include cross-linked polymer, the hydrophilic polymer of preferably micro- crosslinking.Though So these polymer generally can be non-ionic, cationic, zwitterionic or anion, it is preferable that polymer It is cation or anion.

Preferably, precursor super-absorbent polymer particles include acid polymer, which includes multiple acid functional groups, all Such as carboxylic acid group or its salt, particular certain cancers.

Preferably, precursor super-absorbent polymer particles include polyacrylic acid or its salt or polyacrylate or derivatives thereof Cross-linked polymer.

Suitable precursor super-absorbent polymer particles can for example by such as United States Patent (USP) 4,340,706 and United States Patent (USP) 5,849, The reaction of inverse suspension polymerization described in 816 obtains, or by such as U.S. Patent application 2009/0192035,2009/0258994 It is obtained with spraying or other gas phase dispersion polymerization reactions described in 2010/0068520.In some embodiments, suitable Precursor super-absorbent polymer particles can be obtained by the production technology of this field at this stage, such as more specifically by WO 2006/ Described in the 23rd row to the 27th row of page 20 of page 083584,12.

The surface of precursor super-absorbent polymer particles can be coated.The surface of precursor super-absorbent polymer particles can be surface Crosslinking.

Precursor super-absorbent polymer particles may include the crosslinking agent as described below for being used for solution.Preferably, precursor super-absorbent Polymer beads include the crosslinking agent of the first kind.

Precursor super-absorbent polymer particles may include the polymerization initiator system as described below for being used for solution.

Solution

Solution includes the clay platelet being evenly dispersed therein, which has opposite base's platelet surface and piece Crystal edge edge, one or more surface modifying compounds and/or edge modified compound and polymerisable monomer and/or oligomer or Crosslinkable polymer.

Solution may include water.In addition to water, solution also may include other solvent, such as organic solvent.

The concentration of clay platelet in the solution is smaller than based on the weight of dispersion 20%, or less than the weight for pressing dispersion Meter 10%, or less than based on the weight of dispersion 5% or less than based on the weight of dispersion 1%.

Clay and clay platelet

Present invention application clay, the clay can be used as platelet and be dispersed in solution such as acidic aqueous liquid.Solution can be What is neutralized is liquid, aqueous.Solution can be the acidic aqueous liquid of neutralization.Clay particle is with out to out and smallest dimension The form of platelet, such as removing or the individual clay particle of platelet form.For example, out to out and smallest dimension ratio can be At least 2:1 or at least 10:1 or at least 25:1, at most 200:1 or at most 500:1.

Clay platelet in solution is preferably evenly dispersed, for example, there is no the significant aggregations or flocculation of clay platelet.

Clay platelet has edge surface (also referred to as " edge ") and opposite base's platelet surface (also referred to as " table Face ").Clay platelet is that surface is modified and/or edge is modified.This ensures that clay platelet is dispersed in solution.Specifically, When clay platelet very little, clay platelet has low aspect ratio.It is to have very much with the modified clay platelet in surface and/or edge Benefit, so as to the risk for avoiding clay platelet from assembling in the solution.

According to X-ray microscope for example by the use of the Zeiss 810 Ultra 3D X-ray microscope of Xradia sold Or by using dynamic light scattering test method, the modified clay platelet of clay platelet and surface and/or edge in solution Can have less than 800nm, preferably less than 500nm, even more preferably less than 300nm, even more preferably less than 200nm, it is even more excellent Selection of land is less than the equal maximum particle size scale (length) of weight of 100nm.

Dynamic light scattering test method is described in following article: Karpovich, A et al., " Determination of dimensions of exfoliating materials in aqueous suspensions”,MethodsX,2016, 3,19-24.NMR relaxation test method also can be used, and be described in same article above.

According to X-ray microscope for example by the use of the Zeiss 810 Ultra 3D X-ray microscope of Xradia sold Or by using dynamic light scattering test method, the modified clay platelet of clay platelet and surface and/or edge in solution Can have at least 5nm, preferably at least 10nm, the more preferably at least equal maximum particle size scale (length) of the weight of 20nm.

When clay platelet has large scale scale, it may be advantageous to assessment it is as described above they weight most Larger size clay platelet is destroyed by using ultrasonic treatment before big granularity scale.

Clay platelet and surface and/or edge modified clay sheets crystalline substance in solution can have less than 300, preferably less than 200, even more preferably less than 100 aspect ratio.Clay platelet and surface in solution and/or brilliant vertical of edge modified clay sheets Horizontal ratio is typically larger than 5, preferably greater than 10.

The aspect ratio of clay platelet is the out to out of clay platelet and the ratio of orthogonal lowest scale.

In the solution, clay platelet can be used as independent platelet presence or can be used as such as 2 to 5 the small of clay platelet and gathers Collective exists, this can remove the microplate of the super-absorbent polymer particles of agglomeration by (via ultramicrotome), then makes this micro- Piece is subjected to cryo-TEM method known in the art or is determined by using dynamic light scattering test method.

Clay platelet can be purified before surface is modified and/or edge is modified by methods known in the art, such as To remove metal etc..For example, clay to be modified can be dioctahedron or trioctahedral clays.

The example of suitable clay platelet is selected from: kaolinite such as kaolin, illite such as glauconite or terre verte or packet Include montmorillonite, hectorite (i.e. synthesis of clay), saponite, vermiculite or their mixture of hectorite.

Preferably, clay platelet is montmorillonite, hectorite, hectorite or their mixture.

Preferably, clay platelet is hectorite.

Clay platelet has the edge of modified substrate surface and/or modification.The surface of clay platelet and/or edge are modified Can be carried out before addition polymerisable monomer and/or oligomer or crosslinkable polymer, or with polymerisable monomer and/or oligomeric The addition of object or crosslinkable polymer carries out simultaneously.It is brilliant to obtain surface and/or edge modified clay sheets, it can be by clay platelet point It dissipates in the solution comprising one or more surface modifying compounds and/or edge modified compound, and/or can be by clay Platelet is scattered in solution, then optionally the dispersion also can be added as solution or dispersion in one or more modified compounds In body.

The ratio of clay platelet and one or more surface modifying compounds and/or edge modified compound can 1:1 extremely (by weight, based on dry clay platelet and one or more dry edges and/or surface modified compound in the range of 100:1 The poidometer of object).

Hereinafter, one or more surface modifying compounds and/or edge modified compound are with their addition clay flakes It is described before in crystalline substance.

One or more edge modified compounds

When the edge to clay platelet is modified, the exchangeable cations of clay flake crystal edge edge can be by one or more edges Modified compound replacement.Then, the point of zero electric charge of clay flake crystal edge edge, which is typically moved into lower pH value or edge charges, becomes non- The negative electrical charge of neutral charge or non-TCP friendly flow that pH is relied on.

Additionally or alternatively, edge modified compound can be the compound for hindering and reducing the aggregation of clay platelet.

One or more edge modified compounds can be made of one or more phosphorylated compounds.One or more phosphoric acid Changing compound can be selected from: phosphate and/or its derivative and/or its sour form；The phosphate of condensation and/or its derivative and/ Or its sour form；Phosphonic acids, its derivative and its salt；And their combination.For example, ten hydration pyrophosphoric acids can be properly used Sodium.Derivative of organic phosphorus can also be used.

One or more edge modified compounds can be by one or more silanized compounds (also referred to as silane chemical combination Object) composition.

Silanized compounds can be organic silane compound, such as with following formula: SiR^IR^IIR^IIIR^IV, part of R^I、 R^II、R^III、R^IVIt each is selected from following subgroup: a) alkyl, aryl, alkyl, alkene, alkenyl；And b) alkoxy, hydrogen, toluene Sulfonyl contains sulfonyl moieties, chloride ion, halogen ion；And c) hydroxyl, contain carboxy moiety, part containing epoxy group, precondition It is that at least one portion is selected from subgroup b) or subgroup c), and is no more than three parts and is selected from the subgroup a).

Preferably, silanized compounds can be organic silane compound, such as with following formula: SiR^IR^IIR^IIIR^IV, middle part Divide R^I、R^II、R^III、R^IVIt each is selected from following subgroup: a) alkyl, aryl, alkyl, alkene, alkenyl；And b) alkoxy, hydrogen, Tosyl contains sulfonyl moieties, chloride ion, halogen ion；And c) hydroxyl, contain carboxy moiety, part containing epoxy group, premise Condition is that at least one is selected from subgroup a) to three parts and at least one portion is selected from subgroup b) or subgroup c).

It may be beneficial that the part R^I、R^II、R^III、R^IVAt least one of be adapted for being integrated to polymerisable monomer or The part of polymerizable oligomers.For example, at least one described part is unsaturated part, such as vinyl.Preferably, a kind of or more Kind edge modified compound is silanized compounds, such as, 7- octenyldimethylamine methoxy silane.

One or more edge modified compounds can be made of one or more fluorinated compounds.Preferably, a kind of or more Kind edge modified compound includes fluoride salt.Preferably, counter ion counterionsl gegenions M is monovalence counter ion counterionsl gegenions, such as sodium or ammonium.

One or more edge modified compounds can be such compound: except to clay edge it is charge-modified it Outside, the agglomeration at the platelet edge is hindered, spatially to reduce the risk of clay platelet agglomeration in the solution.

One or more edge modified compounds can have at least one at least 10 angstromsOr at least 15 angstroms or at least 20 angstroms Part.Preferably, one or more edge modified compounds have at least one portion, which has at least six carbon former The carbochain of son or at least nine carbon atom or at least 12 carbon atoms.

Other compounds modified for the edge to clay platelet include epoxides.For example, polyethers clay can be formed Platelet.

Preferably, one or more edge modified compounds are by one or more phosphorylated compounds, silanized compounds Or fluorinated compound or their combination form.

Edge modified compound is especially described above as those of phosphorylation, silanization or fluorinated compound, can have Ion or one or more other parts of monomer or oligomer or formed polymer can be covalently bound to；For example, edge changes Property compound can have one or more unsaturated parts (such as with C=C group) and/or one or more can with monomer, The carboxyl of its oligomer or polymer forms the part of ester or amido bond, such as oligo-ether or polyether moiety.To edge modificationization It closes object and is not only joined to the edge of clay flake crystalline substance, and one or more compounds also ion or can be covalently bound to the polymerization Object.

Clay platelet can be not only modified by edge it is evenly dispersed to ensure, but also edge modification can also be used in clay platelet Securely for example covalently or ions binding is to polymerisable monomer and/or oligomer or crosslinkable polymer.

One or more surface modifying compounds

One or more surface modifying compounds can be with cationic portion (and/or: in this paper liquid and this paper Is cation under reaction pH) compound, which can be integrated to the brilliant electronegative substrate surface of clay flake.Surface Modified clay can have one or more electroneutral surfaces (at the pH of carrier liquid).

One or more surface modifying compounds may include alkylation nitrogen part or alkoxylate nitrogen part, including for example straight Chain, branching or cricoid amino-compound, ammonium compounds.Most of parts can be cation at reaction liquid/reaction pH.

One or more surface modifying compounds can have one or more parts, which is selected from amine or imines, including Its derivative such as diamines or diimine and/or its ethylene or polyethylene or oligomerisation of ethylene derivative, including hexamethylene diamine and its derivative Object, ethylenediamine and its derivative, the polyethyleneimine of oligomeric alkene imines and its derivative such as straight chain or branching, oligomeric ether amines and Or mixtures thereof its derivative, straight chain or the amide of branching,.

One or more surface modifying compounds can have acrylamide part.One or more surface modifying compounds can With carbamate moiety (connecting electronegative substrate surface by hydrogen bond) or its further modifier.Preferably, Yi Zhonghuo A variety of surface modifying compounds can have cation-modified carbamate moiety.

Particularly preferably it is selected from following part: straight chain or branched polyethylene imine, hexamethylene diamine or ethylenediamine or any of these Derivative or their mixture.

One or more surface modifying compounds can also be cation-modified oligosaccharide or polysaccharide or derivatives thereof.

In addition, one or more surface modifying compounds can have one or more hydrophilic other parts.This can The modified clay of auxiliary surface is scattered in solution, and/or the super-absorbent polymer particles of agglomeration can be further enhanced Hydrophily, thus affinity of the enhancing to hydrophilic fluid (such as urine, blood, salt water).This can be such as anion part Or-OH.Preferably, one or more surface modifying compounds have at least one for allcoxylated moiety, Carboxylation part or The part of sulphonated portion or sulfated moieties, further to improve hydrophily.

One or more surface modifying compounds can be it is such, when chemical bonding (such as electrostatical binding) arrive clay flake When brilliant surface, they introduce one or more steric hindrances part, hinder the aggregation for reducing clay platelet.To one Kind or a variety of surface modifying compounds can have the part for spatially hindering aggregation.Preferably, one or more surfaces are modified The part that there is compound one or more can provide steric hindrance, the steric hindrance is at least six carbon atom and/or at least 10 angstroms or at least 15 angstroms of length.Preferably, one or more surface modifying compounds have oligomer chain part.

For example, one or more surface modifying compounds can have the part oligomeric alkylene oxide (AO), such as oligomeric ethylidene The part oxygen (EO), at least two or at least five or at least ten, and at most 100 or at most 60 or at most 40 Average AO (such as EO) number of repeat unit.Preferably, one or more surface modifying compounds have at least one portion, should Part is the oligomeric ethoxylate with 2 to 40 number of repeat unit.

One or more surface modifying compounds especially have those of cation group as described above, and can have can Ion is covalently bound to monomer or oligomer or one or more other parts by its polymer formed；For example, surface Modified compound can have one or more unsaturated parts (such as with C=C group) and/or one or more can be with list The carboxyl of body, its oligomer or polymer forms the part of ester or amido bond, such as oligo-ether or polyether moiety.To which surface changes Property compound be not only joined to clay flake crystalline substance surface, and one or more compounds can also ion or to be covalently bound to this poly- Close object.Therefore, clay platelet is not only surface-modified evenly dispersed to ensure, and surface it is modified be also used to it is for example total securely Valence or ions binding are to the polymer.Surface modifying compound as described above such as has the compound of cation group can example It such as include polymerizable moiety, such as alkylidene, such as ethylidene；And/or unsaturated part can be the ester and/or third of such as acrylic acid The alkyl derivative of olefin(e) acid such as methacrylic acid.

During surface and/or edge modification procedure and/or in surface and/or edge modification procedure, ultrasound treatment step And/or it may be useful for applying after mixing step；Preferably apply (such as high) shear-mixed.Such as it is able to use Y- Tron blender.Can also by using high-shear mixer (such as CB Loedige blender, Schugi blender, Littleford blender, Drais blender) influence clay platelet removing.The tip speed of any such blender can be For example, at least 20ms^-1Or at least 30ms^-1To such as 45ms^-1Or 40ms^-1Or 35ms^-1。

The surface of clay platelet and/or edge modification can be realized in any liquid.It can be realized in such as water.Optionally Ground, surface and/or edge modification can realize in the absence of water, such as preferably in anhydrous liquid such as dielectric constant Greater than 40, realized in preferably more than 50 anhydrous liquid such as propene carbonate, ethylene carbonate.Preferably liquid phase may include By weight at least 80% water, preferably by weight at least 90% or even by weight 100% water.

Preferably, one or more surfaces and/or edge modified compound with polymerisable monomer and/or oligomer or can It is lamellite modified to clay before cross-linked polymer mixing.It may be preferred that with polymerisable monomer and/or oligomer or can hand over Before linked polymer mixing, surface to clay platelet and/or edge are modified, and it is brilliant to be washed out gained modified clay sheets, and/ Or filtering and/or dialysis modified clay sheets it is brilliant.

Polymerisable monomer and/or oligomer or crosslinkable polymer

Solution may include polymerisable monomer and/or oligomer, and the polymerisable monomer and/or oligomer include multiple functions Group, such as charge groups (anion, cation) such as carboxylic acid group or its salt, preferably sodium salt.

Preferably, polymerisable monomer and/or oligomer include acrylic acid or its salt or acrylate or derivatives thereof can Polymerized monomer and/or oligomer.

Polymerisable monomer and/or oligomer may include such as ethylenic unsaturated carboxylic acid or its salt, such as acrylic acid, methyl Acrylic acid, maleic acid, fumaric acid, three carboxy vinyls, itaconic acid, ethylenic bond unsaturation phosphonic acids or its salt, ethylenic bond unsaturation sulphur Acid or its salt, or derivatives thereof, acrylamide, Methacrylamide such as with 2- acrylamide-2-methylpro panesulfonic acid, Acrylate and methacrylate.

Preferably, polymerisable monomer and/or oligomer are selected from ethylenic unsaturated carboxylic acid such as methacrylic acid or its salt Or acrylic acid or its salt, ethylenic bond unsaturation phosphonic acids or its salt, ethylenic bond unsaturated sulfonic acid or its salt or their mixture.

Acrylic acid or its salt and methacrylic acid or its salt are particularly preferred polymerisable monomer and/or oligomer.Propylene Acid or its salt are most preferred.

The preparation of available polymerisable monomer and/or oligomer be described in DE-A 199 41 423, EP-A 686 650, In WO 01/45758 and WO 03/14300.

Polymerisable monomer and/or oligomer can be at least 1 weight % to 90 weight %, preferably 10 weight % to 60 weights The content of % is measured in solution.

Other than polymerisable monomer and/or oligomer, solution also may include it is one or more can with polymerisable monomer and/ Or the polymerizable alkylene keyed and/or allyl formula unsaturated monomer of oligomer copolymerization, it can ethylenical unsaturated acids functionalization Monomer.The example of copolymerizable ethylenically unsaturated monomers can be acrylamide, Methacrylamide, crotonamide, metering system Sour dimethylaminoethyl, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, propylene Sour dimethylamino butyl ester, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, acrylate are new Pentyl ester and dimethylaminoethyl peopentyl ester.

Alternatively, solution may include crosslinkable polymer.Preferably, solution includes crosslinkable polymer.Crosslinkable polymeric Object may include polyvinyl alcohol, polyvinylpyrrolidone, starch, starch derivatives, polyethylene glycol, polyacrylic acid, polyvinylamine or Polyallylamine, the polyvinyl formamide of partial hydrolysis or polyvinylacetamide.Preferably, crosslinkable polymer is poly- third Olefin(e) acid or its salt or polyacrylate or derivatives thereof.

Crosslinkable polymer, which can have, is greater than 8,000g/mol by what gel permeation chromatography measured, preferably 10, 000g/mol to 1, within the scope of 000,000g/mol, more preferably within the scope of 50,000g/mol to about 750,000g/mol, very To the weight average molecular weight more preferably within the scope of 90,000g/mol to 700,000g/mol.

In addition to polymerisable monomer and/or oligomer or crosslinkable polymer, solution also may include neutralizer.In can be used And agent, such as alkali metal hydroxide, alkali metal oxide, alkali carbonate or alkali metal hydrogencarbonate and they Mixture.Neutralizer can be ammonia or amine derivative, such as ethanol amine, diethanol amine, triethanolamine or dimethyl aminoethanol amine. Sodium and potassium can be used as alkali metal salt.Preferably, neutralizer is sodium hydroxide, sodium carbonate or sodium bicarbonate and their mixing Object.In general, neutralization is and with aqueous solution or aqueous dispersion or fusant or solid matter blending neutralizer It realizes.The acid groups of the acid groups or crosslinkable polymer of polymerisable monomer and/or oligomer are usually 0-100 moles of %, excellent 25-100 moles of % of selection of land, more preferably 65-90 moles of %, and most preferably 68-80 moles of % is neutralized.

Solution also may include cosolvent.Technically highly useful cosolvent is C₁-C₆-ol such as methanol, ethyl alcohol, n- third Alcohol, isopropanol, n-butanol, sec- butanol, tert-butanol or 2- methyl-1-propyl alcohol, C₂-C₅Glycol such as ethylene glycol, 1,2- the third two Alcohol, 1,3-PD or 1,4-butanediol, ketone such as acetone or carboxylate such as ethyl acetate.

Solution also may include additive, such as polyethylene glycol, polypropylene glycol, mixing poly-alkoxyl compound, be based on polyol Poly-alkoxyl compound, trimethylolpropane or butanediol, the HLB of such as glycerol are greater than the 10 more Portugals of surfactant such as alkyl Glucosides or ethoxylation sugar ester such as polysorbate.Additive can reduce the super of the agglomeration obtained by method described herein The hardness or brittleness of absorbent polymer particles.

The crosslinking agent of the first kind

Solution may include the crosslinking agent of the first kind.The crosslinking agent of the first kind may include institute in such as EP-A 530 438 Ethylene glycol dimethacrylate, diethylene glycol diacrylate, allyl methacrylate, the trimethylolpropane tris propylene stated Acid esters, triallylamine, tetraallyloxyethane, such as EP-A 547 847, EP-A 559 476, EP-A 632 068, WO 93/21237, dipropyl described in WO 03/104299, WO 03/104300, WO 03/104301 and DE-A 103 31 450 Olefin(e) acid ester and triacrylate, the mixed acrylate as described in DE-A 103 31 456 and DE-A 103 55 401 (it not only includes acrylate group, further includes ethylenically unsaturated groups) such as DE-A 195 43 368, DE-A 196 46 484, crosslinker mixture described in WO 90/15830 and WO 02/32962.

Preferably, the crosslinking agent of the first kind includes acrylate or acrylamide group.

When solution includes the crosslinking agent of the first kind, solution also includes polymerizable monomer and/or oligomer.

Preferably, solution includes the crosslinking agent of the first kind with polymerisable monomer and/or oligomer.

Preferably, solution includes acrylate or acrylamide group with polymerisable monomer and/or oligomer.

Preferably, the crosslinking agent of the first kind is diacrylated, dimethacrylated, three propylene acidification or trimethyl The multiple ethoxylated glycerols and/or propoxylated glycerol of propylene acidification.The diacrylate of 3- to the 10- glycerol of ethoxylation again Ester and/or triacrylate are especially advantageous.It is highly preferred that the crosslinking agent of the first kind be 1- to 5- again ethoxylation and/ Or the diacrylate or triacrylate of propoxylated glycerol.

When solution includes the crosslinking agent of the first kind, solution also may include that polymerization initiator system is anti-to cause polymerization It answers.

The polymerization initiator system can be added in solid or liquid form, such as the solution or dispersion in liquid, Such as it is liquid, aqueous, such as water.

The polymerization initiator system may include that the compound of more than one type carrys out initiated polymerization or it may include The compound of single type.

Polymerization initiator system may include activator such as activator compound, such as heat or radiation, including light spoke It penetrates.Alternatively, it may be unnecessary to activate.

Polymerization initiator system can be conveniently selected from conventional (such as free radical) polymerization initiator (and optional catalyst). Preferred display goes out superior water dispersibility/deliquescent material.Polymerization initiator system may include peroxide, hydroperoxides, Hydrogen peroxide, persulfate, azo-compound and redox initiator.Available organic peroxide is such as acetylacetone,2,4-pentanedione Peroxide, methyl-ethyl-ketone peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, peroxidating neopentanoic acid Tertiary pentyl ester, peroxy pivalate, the new caproic acid tertiary butyl ester of peroxidating, peroxidating isobutyric acid tertiary butyl ester, peroxide Change -2 ethyl hexanoic acid tertiary butyl ester, peroxidating isononanoic acid tertiary butyl ester, peroxidating maleic acid tertiary butyl ester, perbenzoic acid Tertiary butyl ester, dicetyl peroxydicarbonate two (2- ethylhexyl) ester, dicetyl peroxydicarbonate dicyclohexyl ester, dicetyl peroxydicarbonate two (4- tert-butylcyclohexyl) ester, dicetyl peroxydicarbonate myristyl ester, dicetyl peroxydicarbonate diacetyl base ester, peracid allyl Ester, peroxidating neodecanoic acid cumene base ester, peroxidating -3,5,5 Trimethylhexanoic acid tertiary butyl ester, acetyl butylcyclohexyl sulfo group peroxide Compound, dilauryl peroxide, diphenyl peroxide formic acid and peroxidating neodecanoic acid tertiary pentyl ester.Preferred azo-compound packet Include 2,2'- azodiisobutyronitrile, 2,2'- azo bis- (2,4- methyl pentane nitriles) and the bis- (4- methoxyl group -2,4- two of 2,2'- azo Methyl-pentane-nitrile), especially water-soluble azo initiator, example 2,2'- azo is double-{ 2- [1- (2- ethoxy) -2- imidazoles Quinoline -2- base] propane } dihydrochloride, 2,2'- azo pair-(2- amidine propane) dihydrochloride, bis- [2- (the 2- imidazoles of 2,2'- azo Quinoline -2- base) propane] dihydrochloride and bis- [2- (5- methyl -2- imidazoline -2- base) propane] dihydrochlorides of 2,2'- azo.Very Specifically, it is preferred that bis- [2- (2- imidazoline -2- base) propane] dihydrochlorides and 2 of 2,2'- azos, the bis- [2- (5- of 2'- azo Methyl -2- imidazoline -2- base) propane] dihydrochloride.

More specifically, polymerization initiator system can be persulfate, such as sodium peroxydisulfate, potassium peroxydisulfate and mistake Two ammonium sulfate of oxygen；Hydroperoxides such as tert-butyl hydroperoxide and cumene hydroperoxide；Such as with azo-compound 2,2'- azo double -2- amidine propane hydrochloride such as VA-044, V-50 and V-501 are (by Wako Pure Chemical Industries Ltd. production) and Fe²⁺Mixture；And hydrogen peroxide or hydrogen peroxide and ascorbic acid.It can be used One of mixture of two or more polymerization initiators, such as azo compounds species and peroxide or peroxide compound One of.It is believed that this ensures rapid polymerization.As described in US2008/242817, to control polymerization rate, azo is used Compound initiator or redox initiator are advantageous.

Polymerization initiator system can based on the weight of polymerisable monomer at least 0.001%, preferably press polymerisable monomer Poidometer at least 0.01%, more preferably at least 0.02%, at most 0.1%, content preferably no more than 0.05% introduces.

Polymerization rate can be controlled with amount and temperature used by polymerization initiator compound itself used.

Also it may be present polymerization catalyst, such as TMEDA (N, N, N ', N '-tetramethylethylenediamine).The polymerization of polymerisable monomer Can high exothermic heat, therefore polymeric liquid can be cooled down during polymerization.

The crosslinking agent of Second Type

Alternatively or in addition to the crosslinking agent for using the first kind, solution also may include the crosslinking agent of Second Type.Second The crosslinking agent of type may include the group that can form covalent bond with the carboxylate group of polymer containing two or more Compound.Available compound includes for example as described in EP-A 083 022, EP-A 543 303 and EP-A 937 736 Polyglycidyl compounds, polyaziridine, polyamine, polyamidoamines amine, diglycidyl or poly epihydric alcohol base chemical combination Object, the polyalcohol as described in DE-C 33 14 019.The crosslinking agent of Second Type may include from 40 20 780 ring of DE-A Shape carbonic ester comes from 198 07 502 2- oxazolidone of DE-A and its derivative (such as N- (2- hydroxyethyl) -2- oxazolidine Ketone), from DE-A 198 07 992 2-and poly- 2- oxazolidone, come from 198 54 573 2- oxo tetrahydro-1,3- of DE-A Oxazines and its derivative, from 198 54 574N- acyl group -2- oxazolidone of DE-A, from 102 04 937 ring urea of DE-A, From 103 34 584 bicyclic amide acetal of DE-A, 1 199 327 oxetanes of EP-A and ring urea are come from, and comes from WO 03/031482 morpholine -2, the compound of 3- diketone and its derivative.

The crosslinking agent of preferred Second Type is amide acetals, carbamate, polyalcohol such as glycol or polyol, cyclic annular carbon Acid esters, double oxazolines, epoxides or glycidol ether such as ethylene glycol diglycidylether.

The crosslinking agent of preferred Second Type is glycidol ether, such as ethylene glycol diglycidylether.

When solution includes the crosslinking agent of Second Type, solution also includes crosslinkable polymer.

Preferably, solution includes the crosslinking agent of the Second Type with crosslinkable polymer.

Preferably, solution includes glycidol ether, such as with the ethylene glycol diglycidylether of crosslinkable polymer.

Solution may include the crosslinking agent of Second Type, and the poidometer based on solution, content is in 0.001 weight % to 30 weights In the range of measuring %, preferably in the range of 0.01 weight % to 15 weight %, more preferably in 0.02 weight % to 7 weights In the range of amount %.

Comprising clay platelet and polymerisable monomer and/or oligomer with modified surface and/or edge or cross-linking The solution of polymer can have according to ASTM 1824/90 measure at about 20 DEG C in 50mPa.s to 50,000mPa.s range It is interior, preferably within the scope of 100mPa.s to 20,000mPa.s, more preferably within the scope of 100mPa.s to 5,000mPa.s Viscosity.

The high viscosity of solution comprising polymerisable monomer and/or oligomer or crosslinkable polymer makes adjacent precursor superabsorbent Pinching polymer beads can be fixed together when mixing with solution as described above at specific contact point between particles.Cause This, precursor super-absorbent polymer particles are not completely coated with solution, but since only contact is molten at specified point for the viscosity of solution Liquid.At these specific contact points, the high viscosity of solution is capable of fixing adjacent precursor super-absorbent polymer particles together To form the super-absorbent polymer particles of agglomeration.Adjacent precursor super-absorbent polymerization in the super-absorbent polymer particles of agglomeration Relatively strong bonding is formed between composition granule.

Solution may include clay platelet, 5 weights with modified surface and/or edge of 0.1 weight % to 10 weight % Measure the water of % to 95 weight %；Polymerisable monomer and/or oligomer, the 0.001 weight % to 10 weights of 5 weight % to 95 weight % Measure % the first kind crosslinking agent, optional dispersing aid and 0.001 weight % to 5 weight % polymerization initiator with Start polymerization reaction.

Alternatively, solution may include the clay flake with modified surface and/or edge of 0.1 weight % to 10 weight % Brilliant, 5 weight % to 95 weight % water；Crosslinkable polymer, the 0.001 weight % to 10 weights of 5 weight % to 95 weight % Measure the crosslinking agent and optional dispersing aid of the Second Type of %.

The super-absorbent polymer particles of agglomeration

The present invention relates to the super-absorbent polymer particles of agglomeration.It has surprisingly been found that using comprising having modified table The solution of the clay platelet in face and/or edge provides the super-absorbent polymer particles of the agglomeration of opposite high yield, which has Quick initial absorption speed, while also there is good capacity.

The clay platelet with modified surface and/or edge for being connected to precursor super-absorbent polymer particles is kept centainly Power can increase the elongation at break of the super-absorbent polymer particles of agglomeration.When precursor super-absorbent polymer particles depositing in body fluid In lower swelling, the super-absorbent polymer particles comprising the agglomeration with modified surface and/or the clay platelet at edge therefore can Better against deformation to avoid or reduce gel adhesion.

In addition, the clay platelet with modified surface and/or edge avoids the agglomeration of clay platelet, to improve agglomeration Super-absorbent polymer particles elongation at break and improve infiltration rate of the super-absorbent polymer particles to body fluid of agglomeration.

In fact, the super-absorbent polymer particles of agglomeration of the invention can form the agglomerate being less compacted, while still mentioning For stable agglomerate.Due to the viscosity comprising the solution with modified surface and/or the clay platelet at edge, precursor super-absorbent Polymer beads can be fixed to one another at only specific contact point, to avoid the compacting of agglomerate.Mode by comparing, it is sufficient to The reduced contact area for forming stable agglomerate is similar to using relatively strong glue to be bonded to one another different surfaces.Relatively In obtain can bond strength by comparison need high surface area coverage rate when weaker glue, can be in smaller surface district Stronger glue is provided on domain.

Reduced contact area and reduced compacting can lead to when in use, such as when by the super-absorbent polymer of agglomeration When grain is in absorbent article, the more surface area absorbing liquid body of the super-absorbent polymer particles of agglomeration.This then causes to have There are the super-absorbent polymer particles of the agglomeration of opposite high-selenium corn speed, this initial fluid in the super-absorbent polymer particles of agglomeration It can be and be especially desired to when intake, as reflected by the low intake time.

When the super-absorbent polymer particles of agglomeration have lower than 850 μm of size, be preferably ranges between 300 μm and 850 μm it Between size when, according to free swell rate (FSR) test method described below, the super-absorbent polymer of agglomeration of the invention Particle can have greater than 1.00g/g/s, preferably more than 1.05g/g/s, and more preferably larger than 1.10g/g/s's reaches 20g/g Average swelling rate.

When the super-absorbent polymer particles of agglomeration have higher than 850 μm of size, be preferably ranges between 850 μm and 1250 μm it Between size when, according to free swell rate (FSR) test method described below, the super-absorbent polymer of agglomeration of the invention Particle can have greater than 0.50g/g/s, preferably more than 0.75g/g/s, and more preferably larger than 0.90g/g/s's reaches 20g/g Average swelling rate.

Compared with the absorbent article of the prior art, especially first shove when (that is, when the first liquid intrusion), comprising tool Having the absorbent article of the super-absorbent polymer particles of the agglomeration of good swelling rate and low intake time has improved absorption special Property, and therefore show reduced leakage.Therefore, the super-absorbent polymer particles of such agglomeration are made especially suitable for absorbing Product.

The super-absorbent polymer particles of agglomeration of the invention can have following permeability: according to UPM test method, balance When indicated with UPM (urine permeability measurement) value, be greater than 5, preferably more than 15, preferably more than 30, preferably more than 40, more Preferably more than 60, more preferably larger than 70, or even more preferably greater than 80UPM unit, wherein 1UPM unit is 1 × 10^-7 (cm³.s)/g。

The super-absorbent polymer particles of agglomeration of the invention can have following permeability: according to following UPM test methods, In It is indicated when balance with UPM (urine permeability measurement) value, 40UPM to 500UPM, preferably 50UPM to 400UPM, more preferably 80UPM to 400UPM.

UPM test method measures the flow resistance of the pre-swollen layer of super-absorbent polymer particles, that is, flow resistance is balancing When or close to balance when measure.Therefore, the super-absorbent polymer particles of the agglomeration with high UPM value show Thief zone Property.When the absorbent article of a large amount of volumes is soaked by liquid efflunent, high osmosis is particularly desired in absorbent article. These absorbent articles not only show good absorption characteristic when first shoves but also when then shoving.

In addition, the super-absorbent polymer particles of Centrifuge Retention Capacity (CRC) measurement agglomeration free swell in excess liq The liquid absorbed.

As measured according to CRC test method (EDANA method NWSP 241.0.R2), the super-absorbent of agglomeration of the invention Polymer beads can have greater than 20g/g, preferably more than 25g/g, preferably more than 26g/g, more preferably larger than 27g/g, Or Centrifuge Retention Capacity (CRC) value of even more preferably greater than 29g/g.

As measured according to CRC test method (EDANA method NWSP 241.0.R2), the super-absorbent of agglomeration of the invention Polymer beads can have 18g/g to 40g/g, and the centrifugation of preferably 22g/g to 40g/g, more preferably 25g/g to 38g/g are protected Retention capacity (CRC) value.

It can be prepared as follows the super-absorbent polymer particles of agglomeration of the present invention:

A) providing has the first mass average particle size¹The precursor super-absorbent polymer particles of mAvPS:

In addition, for the present invention, precursor super-absorbent polymer particles are (with regard to the first mass average particle size¹For mAvPS) Or the super-absorbent polymer particles of agglomeration are (with regard to the second mass average particle size²For mAvPS) quality average particle size be defined as grain Degree, the granularity be given precursor super-absorbent polymer particles (or super-absorbent polymer particles of agglomeration) being averaged by mass Granularity.Method for quality measurement average particle size is described below in Test Methods section.Precursor super-absorbent polymer particles The quality average particle size of (or super-absorbent polymer particles of agglomeration) can be 45 μm to 850 μm or 100 μm to 650 μm, or 200 μm to 600 μm, as long as the second mass average particle size²MAvPS is than the first mass average particle size¹MAvPS high at least 25%.

With the first mass average particle size¹The precursor super-absorbent polymer particles of mAvPS can be any precursor super-absorbent Polymer beads.However, it may be desirable to use categorized precursor super-absorbent polymer particles.For example, precursor superabsorbent pinching Polymer beads can be classified so that it has the upper size boundary limited.Upper size boundary can for 500 μm or 400 μm or 300 μm, Or 150 μm.

Classification is well known in the art and is usually carried out by using the mesh size screening particle of restriction.It is logical The particle of sieving can have a granularity lower than mesh size used, however the particle of obstructed sieving (major part) is had be equal to or Greater than the granularity of mesh size.As it will be appreciated, if too many precursor super-absorbent polymer particles sieve simultaneously, obstructed sieving Precursor super-absorbent polymer particles in some granularities that can still have less than mesh size.Therefore, such as by art technology What personnel were understood, it is important that do not use too many precursor super-absorbent polymer particles once, carefully and hardy sieved Point.

In addition, the shape of the super-absorbent polymer particles of precursor super-absorbent polymer particles or agglomeration to be sieved also influences The precision of screening.For having the very particle or agglomerate of irregular shape, their current orientations can determine that they are It is no to pass through given mesh size.Therefore, screening has the very precursor super-absorbent polymer particles of irregular shape or agglomeration Super-absorbent polymer particles can lead to relatively high standard deviation.As it will appreciated by a person of ordinary skill, in such case Under, it is thus possible to expectation increases the repeatability of screening or increases sample number.

Therefore, because the classification by using screening obtains, upper size boundary as used herein and granularity lower limit will be managed Solution are as follows: for upper size boundary, the super-absorbent polymer particles of corresponding precursor super-absorbent polymer particles or agglomeration may include By weight at most 10%, or at most 5% precursor super-absorbent polymer particles with granularity more higher than upper size boundary or The super-absorbent polymer particles of agglomeration.For granularity lower limit, the superabsorbent of corresponding precursor super-absorbent polymer particles or agglomeration Pinching polymer beads may include by weight at most 10%, or at most 5% precursor with granularity more lower than granularity lower limit Super-absorbent polymer particles or the super-absorbent polymer particles of agglomeration.

Other than being categorized into precursor super-absorbent polymer particles with upper size boundary, it is also possible to expectation further classification Precursor super-absorbent polymer particles, which make them also, has granularity lower limit.Granularity lower limit can be 20 μm or 30 μm or 45 μm or 63 μm or 80 μm.

Difference between the upper size boundary and granularity lower limit of the precursor super-absorbent polymer particles provided in step a) can be with Less than 600 μm or less than 500 μm or less than 300 μm or less than 150 μm.Difference between upper size boundary and granularity lower limit can be with Not less than 20 μm.

Classification can be used to obtain and there is desired first mass average particle size¹The precursor super-absorbent polymer of mAvPS Grain.

The precursor super-absorbent polymer particles of offer can be matrix polymer, i.e., precursor super-absorbent polymer particles without It is successive how surface-crosslinked.Although precursor super-absorbent polymer particles can also be surface-crosslinked and/or can however, less desirably Other processing are undergone, are such as coated.

It in general, is that desired dry precursor super-absorbent polymerize according to the precursor super-absorbent polymer particles that step a) is provided Composition granule has based on the weight of precursor super-absorbent polymer particles less than 10%, or presses precursor super-absorbent polymer particles Poidometer less than 5%, or the water content based on the weight of precursor super-absorbent polymer particles less than 3%.However, according to step A) the precursor super-absorbent polymer particles provided can also have higher moisture, such as by weight at most 15%, by weight At most 25%, by weight at most 50% or even higher.

B) by precursor super-absorbent polymer particles with comprising clay platelet, one or more surface modifying compounds and/or The mixing of the solution of edge modified compound and polymerisable monomer and/or oligomer or crosslinkable polymer,

There to be the first mass average particle size¹The precursor super-absorbent polymer particles of mAvPS and include clay platelet, one kind Or a variety of surface modifying compounds and/or edge modified compound and polymerisable monomer and/or oligomer or crosslinkable polymeric The solution of object mixes.

Solution may include water.In addition to water, solution also may include other solvent, such as organic solvent.However, it is expected that removing Any solvent is not used except water.

Precursor super-absorbent polymer particles and the mixing comprising the solution with modified surface and/or the clay platelet at edge It can be with precursor super-absorbent polymer particles at least 1g provided by every kg per minute, or at least 2g, or at least 4g, or at least 6g, or the rate of at least 8g solution carry out.The rate can be for less than 200g/kg/min, or is less than 100g/kg/min.

It can be by that will include that the solution spraying of the clay platelet with modified surface and/or edge polymerize to precursor super-absorbent It is mixed on composition granule.It may expect to stir precursor super-absorbent polymer particles during and/or after applying solution.

Mixing can carry out in setting well known in the art, such as coating machine, dasher, plough share mixer, kneading Machine, fluidized bed coater, Wurster coating machine, rotating disk reactor etc..

Mixing can in room temperature or at high temperature (for example, 30 DEG C to 100 DEG C or so, more preferably 40 DEG C to 70 DEG C or so) into Row.If mixing carries out at elevated temperatures, the super-absorbent polymer particles of resulting agglomeration may sufficiently dry So that not needing subsequent drying steps.However, temperature may not up to evaporate excessive application solution too quickly.

If solution includes the crosslinking agent of the first kind, polymerization procedure will be required.For example, polymerization procedure can be for certainly By base polymerization procedure.

It include precursor super-absorbent polymer by using the polymerization initiator system for being activated to initiated polymerization The crosslinking agent of grain, clay platelet, polymerisable monomer and/or oligomer with modified surface and/or edge and the first kind Mixed solution can be polymerize by any kind of polymerization reaction.Polymerization initiator system can be by applying heat (at 120 DEG C Or higher than 120 DEG C at a temperature of) and/or radiation to activate.After polymerization reaction, the super-absorbent polymer particles of agglomeration are obtained.

If desired, can after polymerization procedure for example for example more than 50 DEG C, more than 100 DEG C, more than 120 DEG C, be more than 180 DEG C or step is dried more than 200 DEG C, or at a temperature of preferably 100 DEG C to 150 DEG C.

If solution includes the crosslinking agent of Second Type, the crosslinking agent of the Second Type be amide acetals, carbamate, Polyalcohol such as glycol or polyol, cyclic carbonate, double oxazolines or epoxides, then polymerization procedure may not be required.Example Such as, free radical polymerization step may not be required.

If solution includes the crosslinking agent of Second Type, cross-linking step is carried out after the mixing step.

Cross-linking step can be with including precursor super-absorbent polymer particles, the clay flake with modified surface and/or edge The mixed solution of brilliant, crosslinkable polymer and Second Type crosslinking agent carries out.

Heating stepses or drying steps at a temperature of cross-linking step can be at 120 DEG C or higher than 120 DEG C.Cross-linking step it Afterwards, the super-absorbent polymer particles of agglomeration are obtained.

If desired, can after cross-linking step for example for example more than 50 DEG C, more than 100 DEG C, more than 120 DEG C, be more than 180 DEG C or step is dried more than 200 DEG C, or at a temperature of preferably 100 DEG C to 150 DEG C.

The super-absorbent polymer particles of agglomeration are obtained by step b) and the advantageously dry agglomeration of optional drying steps Super-absorbent polymer particles.Dry agglomeration super-absorbent polymer particles can have by weight less than 10%, or by weight Meter is less than 5%, or the water content by weight less than 3%.

According to the present invention, the quality average particle size (herein referred to as of the super-absorbent polymer particles of agglomeration obtained Two mass average particle sizes²MAvPS) the first mass average particle size of ratio¹MAvPS high at least 25%, the first mass average particle size be It is subjected to comprising clay platelet and polymerisable monomer and/or oligomer or crosslinkable polymeric with modified surface and/or edge The quality average particle size of precursor super-absorbent polymer particles before the solution of object.Second mass average particle size²MAvPS can compare First mass average particle size¹MAvPS high at least 30% or at least 40% or at least 50%.

If the second mass average particle size after having carried out step b)²MAvPS is than the first mass average particle size¹mAvPS Height can then increase classifying step less than 25% after step b).

By the classifying step, the amount of the super-absorbent polymer particles of non-agglomeration is significantly reduced so that the second mass is average Granularity²MAvPS increases.

After step b), and the optional classifying step carried out after optional drying steps eliminates to have and be lower than The precursor super-absorbent polymer particles of the granularity of granularity lower limit.Optional classifying step and the therefore super-absorbent polymer of agglomeration The granularity lower limit of particle for 150 μm or can be able to be 300 μm or can be 500 μm.

If had been provided by classifying step with the first mass average particle size¹The precursor super-absorbent of mAvPS polymerize Composition granule and there is upper size boundary, then optional point carried out after step b) (and after optional drying steps) The granularity lower limit of class step, for agglomeration super-absorbent polymer particles carry out classifying step granularity lower limit can for First mass average particle size¹80% to 100% or the 90% of the upper size boundary of the precursor super-absorbent polymer particles of mAvPS to 100%.Therefore, in the latter class step, the major parts of the super-absorbent polymer particles of non-agglomeration (or it is substantially all, If (being equal to) that the granularity lower limit of agglomerate is 100% has the upper size boundary of the particle of the first average particle size) it will be sieved It separates and the super-absorbent polymer particles of agglomeration is retained.

If not suffering from any surface-crosslinked precursor superabsorbent pinching before being formed by agglomeration by matrix polymer particle Polymer beads form the super-absorbent polymer particles of agglomeration of the invention, then matrix polymer can obtain as follows:

Acrylic acid polymer gel is provided.Acrylic acid polymer gel can be prepared by well known method, and example Such as can by prepared by polymerizable acrylic monomer, such as by under 50% to 95% degree of neutralization by polymerizable acrylic monomer system It is standby.Neutralization is usually carried out by sodium hydroxide.

So that the gel is subjected to the first grinding steps, be subjected to the first drying steps later to obtain matrix polymer particle,

If matrix polymer particle is too dry for the second grinding steps after the first drying steps, then can appoint Choosing soaks matrix polymer particle again.

Then, matrix polymer particle can be made to be subjected to the second grinding steps, be subjected to the second drying steps later.

Alternatively, grinding steps may not be required.For example, matrix polymer particle can be according to BASF SE's In the WO2012066888A1 of WO2015014826A1, SUMITOMO or method described in the WO2015062883 of BASF SE It obtains.

Before being subjected to the second grinding steps, the water content of matrix polymer particle can be at least 0.4g water/g butt body Polymer beads, but it can be not more than 15g/g, advantageously 0.4g/g to 5g/g or 0.8g/g to 3g/g or 1g/g to 2g/g. Corresponding water content can by the first drying steps by matrix polymer particle it is dry to desired water content levels (that is, Not " complete " dried base polymer beads) it obtains.Alternatively, if the derivative matrix polymerization after the first drying steps Composition granule is too dry, then can soak again they to obtain desired water content before the second grinding steps.

By providing the first and second grinding steps, the matrix polymer particle with relative high surface product may be obtained, Because polymer is exposed to the shearing force in grinder twice.

It is surface-crosslinked

The surface-crosslinked of super-absorbent polymer particles is well known in the art.

The super-absorbent polymer particles of agglomeration can be surface-crosslinked.For the present invention, the super-absorbent polymer of agglomeration Particle it is surface-crosslinked, although or less desirably, before the mixing step for forming agglomerate or with form the mixed of agglomerate Any one of known surface cross-linking process can be passed through by closing the surface-crosslinked of precursor super-absorbent polymer particles of step simultaneously Come carry out.

Common surface crosslinking agent is the surface crosslinking agent of thermal activation.Term " heat-activatable surface crosslinking agent " refers to only The surface crosslinking agent to react when being exposed to high temperature, temperature are usually 150 DEG C or so.For example, well known in the prior art Heat-activatable surface crosslinking agent is such as two functions or multifunctional reagent, can be in the poly- of precursor super-absorbent polymer particles It closes and constructs additional crosslinking between object chain.Other thermal activation surface crosslinking agents include such as dihydric alcohol or polyalcohol or are capable of forming The derivative of they of dihydric alcohol or polyalcohol.The representative of these reagents be alkylene carbonate, ketal and diglycidyl ether or Polyglycidyl ether.In addition, polyglycidyl ether, halogenated epoxide, polyacetals, polyol and polyamine are also well known thermal activation Surface crosslinking agent.Crosslinking is based on the reaction between functional group contained by precursor super-absorbent polymer particles, such as carboxyl (polymer It is contained) and hydroxyl (contained by surface crosslinking agent) between esterification.

In general, due to by precursor super-absorbent polymer particles with comprising viscous with modified surface and/or edge The solution of native platelet and polymerisable monomer and/or oligomer or crosslinkable polymer mixes and is formed the super-absorbent polymerization of agglomeration Before composition granule, period or it is more desirable after, surface crosslinking agent is applied on the surface of precursor super-absorbent polymer particles. Therefore, reaction preferably occurs on the surface of precursor super-absorbent polymer particles or the super-absorbent polymer particles of agglomeration, this Lead to the improved crosslinking on particle surface, while having no substantial effect on the core of particle.(agglomeration) (precursor) super-absorbent as a result, The surface of polymer beads becomes harder.

Surface crosslinking agent organic solvent usually to be made of or solution form comprising organic solvent applies.Compared to using Water generally makes the surface of precursor super-absorbent polymer particles less adhere as solvent, such organic solvent.However, just being formed For the super-absorbent polymer particles of agglomeration, the surface of adhesion is desired, because it promotes agglomeration.Therefore, especially in table Face crosslinking agent, which is applied to, to be made of organic solvent or when solution comprising organic solvent, it may be desirable to due to precursor superabsorbent pinching Polymer beads with comprising the clay platelet and polymerisable monomer and/or oligomer with modified surface and/or edge or can hand over The solution of linked polymer is mixed and is formed after the super-absorbent polymer particles of agglomeration, by precursor super-absorbent polymer particles surface Crosslinking.

However, surface crosslinking agent can in the form of aqueous solution, via gas phase (that is, liquid surface crosslinking agent is evaporated) or It is added by adding in the pure surface crosslinking agent of liquid form.

Surface crosslinking agent can also add together with other materials, such as surfactant.

In general, surface-crosslinked will carry out at least 100 DEG C, or at a temperature of at least 120 DEG C, or at least 150 DEG C.The possible phase It not hopes and increases temperature more than 200 DEG C, or be no more than 180 DEG C, to avoid such as (agglomeration) (precursor) super-absorbent polymer Grain turns yellow.

Absorbent article

The typical disposable absorbent article of the super-absorbent polymer particles of agglomeration of the invention can be used to be close to or neighbouring wear Person body place with absorb and accommodate from body be discharged various effluents and in the form of diaper 20 in Fig. 1 to Fig. 5 Middle expression.

In more detail, Fig. 1 is the plan view of the exemplary diaper 20 in flattened state, and part diaper is removed with more It is clearly shown the construction of diaper 20.The diaper 20 is only shown for illustration purposes, because structure of the invention can quilt It is included in various diapers or other absorbent articles.

As depicted in figs. 1 and 2, absorbent article (being herein diaper) may include that top flat 24, the liquid of fluid permeable can not The egative film 26 of infiltration, the absorbent cores 28 being located between top flat 24 and egative film 26.Absorbent cores 28 are absorbable and accommodate by the suction Receive the received liquid of product, and may include absorbing material 60, the super-absorbent polymer particles 66 of agglomeration such as of the invention and/ Or in cellulose fibre and absorbent article commonly used by (such as the fixed superabsorbent pinching of other absorbing materials and non-absorbing material The thermoplastic adhesives of polymer beads).It is (such as one or more non-woven that absorbing material and non-absorbing material can be wrapped in substrate Object, thin paper) in, such as by facing the upper core cover layer 56 of top flat and facing the lower core cover layer 58 of egative film.On such Core cover layer and lower core cover layer can be made of non-woven fabric, thin paper etc. and can for example along its periphery continuously or discontinuously Ground is attached to each other.

The absorbent cores may include one or more basal layers (such as non-woven webs or tissue paper), be arranged described Super-absorbent polymer particles on one or more basal layers and the thermoplasticity being generally arranged on super-absorbent polymer particles Composition.The usual thermoplastic compounds are thermoplastic adhesive materials.In one embodiment, thermoplastic adhesives material Material forms fibrous layer, and the fibrous layer at least partly contacts the super-absorbent polymer particles on one or more of basal layers And partly contact one or more of basal layers.In order to enhance super-absorbent polymer particles and/or thermoplastic adhesives material Expect that auxiliary binder can be deposited on to one the adhesiveness of respective substrates layer before applying super-absorbent polymer particles Or on multiple basal layers.Absorbent cores may also comprise one or more coatings, so that super-absorbent polymer particles are included in one Or between multiple basal layers and one or more coatings.The one or more basal layer and one or more coatings may include Non-woven webs are made of non-woven webs.Absorbent cores also may include smell control compound.

Absorbent cores can be substantially by one or more basal layers, super-absorbent polymer particles, thermoplastic compounds, optionally Auxiliary binder, optionally coating and optionally smell control compound composition.

Absorbent cores also may include the mixture of super-absorbent polymer particles and airfelt, can be embedded in one or more bases In bottom such as non-woven webs or tissue paper.Such absorbent cores may include based on the weight of the absorbing material 30% to 95% or 50% to 95% super-absorbent polymer particles and may include 5% to 70% based on the weight of the absorbing material, Or 5% to 50% airfelt (for these percentages, the basal layer of any embedding is not considered as absorbing material).Absorbent cores Also can be free of airfelt and may include based on the weight of the absorbing material 100% super-absorbent polymer particles.

Absorbent cores may include the super-absorbent polymer particles of agglomeration of the invention and mixing for other super-absorbent polymer particles Close object.For example, absorbent cores may include based on the weight of the absorbing material at least 70%, or at least 80%, or at least 90% or 100% super-absorbent polymer particles, wherein the super-absorbent polymer particles include by weight at least 10%, or at least The super-absorbent polymer particles of 20% or at least 30% or at least 50% agglomeration.

Absorbent article of the invention, especially diaper and trousers may include the combination of acquisition layer 52, Distribution Layer 54, or both (herein all collectively referred to as acquisition-distribution system " ADS " 50).The function of ADS 50 is usually fluid described in Quick Acquisition and with height Efficacious prescriptions formula is distributed to absorbent cores.ADS may include one, two or more layer.

ADS can be free of super-absorbent polymer.Prior art discloses acquisition-distribution system of many types, see, for example, WO2000/59430,WO95/10996,US5700254,WO02/067809.However, the super-absorbent polymer of agglomeration of the invention Particle can also include by ADS.

The function of Distribution Layer 54 is to make it possible to more have in the larger surface that the fluid body of invasion is distributed in product Effect ground uses the absorptive capacity of absorbent cores.Distribution Layer can by based on synthesize or cellulose fibre and have the non-of relative low density knit Producing material material is made.Distribution Layer can usually have 30g/m²To 400g/m², specifically 80g/m²To 300g/m²Average basis weight.

Distribution Layer can such as crosslinking comprising by weight at least 50% or 60% or 70% or 80% or 90% it is fine Cellulose fiber.Cross-linked cellulose fibres can be fold, twisting or curling or their combination (including rise fold , twisting and curling).Cross-linked cellulose fibres provide under product packaging or use condition (such as under infant weight) The higher elastic and therefore higher incompressible resistance of first absorbed layer.This provides relatively high voidage, permeability to core And liquid absorption, to reduce leakage and improved drying property.

Distribution Layer comprising cross-linked cellulose fibres may include other fibers, but this layer can be advantageously comprised by the layer The cross-linked cellulose fibres of poidometer at least 50% or 60% or 70% or 80% or 90% or even up to 100%.This The example of the mixed cross-linked cellulose fibres layer of kind may include cellulose fibre, the 10 weight % of the chemical crosslinking of 70 weight % The untreated paper pulp fiber of polyester (PET) fiber and 20 weight %.In another example, cross-linked cellulose fibres layer can The PET fiber of the cellulose fibre of chemical crosslinking comprising 70 weight %, the Lyocell fibers of 20 weight % and 10 weight %.Again Such as, this layer may include the untreated paper pulp fiber and 16 weights of the cellulose fibre of the chemical crosslinking of 68 weight %, 16 weight % Measure the PET fiber of %.

Absorbent article 20 may also include acquisition layer 52, function be fluid described in Quick Acquisition make it away from top flat so as to for Wearer provides good drying property.Acquisition layer 52 is often placed directly below top flat and below Distribution Layer.Acquisition layer is usual Can be or including non-woven material, such as SMS or SMMS material, the non-woven material include spunbond layer, meltblown layer and Other spunbond layers alternatively comb chemical bonding supatex fabric into the net.Non-woven material can be specifically by latex binder. Illustrative upper acquisition layer 52 is disclosed in US7786341.Combing resin bonded supatex fabric into the net can be used, especially It is in the case where the fiber used is solid circles or circle and hollow PET staple fiber (for example, 6 denier fibers and 9 50/50 or 40/60 mixture of denier fiber).Exemplary binder is Butadiene/Styrene latex.

Acquisition layer 52 can be by latex adhesive such as styrene-butadiene latex binder (SB latex) Lai Wending.For The method for obtaining such lattice is known, such as is found in 2003/0105190 (Diehl of EP 149 880 (Kwok) and US Et al.).Adhesive can be present in acquisition layer 52 more than 12%, 14% or 16% by weight, but can be by acquisition layer Poidometer, which is no more than 30% or is no more than 25%, to be existed.SB latex can be with trade name GENFLO^TM3160(OMNOVA Solutions Inc.；Akron, Ohio) it obtains.

In addition to above-mentioned first acquisition layer, other acquisition layers also can be used.For example, tissue layers can be placed in the first acquisition layer Between Distribution Layer.Compared with above-mentioned acquisition layer, thin paper can have the capillary distribution character of enhancing.Thin paper and the first acquisition layer There can be identical size or there can be different sizes, such as compared with the first acquisition layer, tissue layers can also be after absorbent article Extend in portion.The example of hydrophily thin paper is 13gsm to 15gsm high wet strength, by the cellulose fibre for being purchased from supplier Havix It is made.

Diaper may also include elastification leg cuff 32 and barrier leg cuff 34, the elastification leg cuff and/or barrier leg cuff improvement pair The constraint of liquid and other body exudates, especially in leg opening area.In general, each leg cuff 32 and barrier hoop 34 will Including one or more elastic filament 33 and 35, the elasticity filament is illustrated in exaggerated form on Fig. 1 and 2.In addition, diaper 20 It may include other feature structure, such as rear auricle 40, preceding auricle 46 and/or the barrier hoop 34 of attachment, to form composite diaper Structure.Diaper may also include fastening system, such as adhesive fastening system or mechanical fastening system (such as hook-loop fastening system System), the fastening system may include band protruding portion 42, such as adhesive tape protruding portion or the band protruding portion including hook element, described Hook element cooperates with touch-down zone 44 (such as providing the non-woven webs of the ring in hook-loop fastening system).In addition, diaper may be used also Including other elements, such as rear elastic waist structure and preceding elastic waist structure, lateral plate or lotion applications.

As illustrated in fig. 1 and 2, diaper 20 can be hypothetically divided into first lumbar region 36, the second lumbar region opposite with first lumbar region 36 38, and the crotch region 37 between first lumbar region 36 and second lumbar region 38.Longitudinal centre line 80 is along its length by diaper point From the imaginary line at two equal half blocks.Cross central line 90 be perpendicular to the vertical line 80 in the plane for the diaper being flattened simultaneously Imaginary line across the centre of diaper length.The periphery of diaper 20 is limited by the outer edge of diaper 20.The longitudinal edge of diaper can The longitudinal centre line 80 for being roughly parallel to diaper 20 extends, and end edge is roughly parallel to the cross central line 90 of diaper 20 vertical Extend between edge.

One or more is substantially free of the region 29 of absorbing material and channel 29 '

As shown in figure 3, absorbent cores 28 may include one or more regions 29 substantially free of absorbing material.So-called " base Be free of on this ", it is intended that in each of these regions, the base weight of absorbing material is that the absorbing material in the remainder of core is flat Equal base weight less than 25%, particularly less than 20%, less than 10%.Specifically, can not have absorbing material in that region. The a small amount of such as unintentional pollutant with absorbing material being likely to occur in the fabrication process is not considered as absorbing material.When When from the point of view of in the plane of core, region 29 is advantageously absorbed material encirclement, this refers to that one or more regions 29 are not extend to Any edge of the deposition region 8 of absorbing material.

Upper core cover layer 56 is wrapped up by these regions 29 substantially free of absorbing material by one or more cores Object binding part 27 is attached to lower part cover layer 58.As shown in Figures 4 and 5, when absorbing material is molten during absorbing liquid When swollen, core wrappage binding part keeps at least initial attachment in region 29 of the one or more substantially free of material.Core Absorbing material in remainder is swollen when it absorbs liquid, so that core wrappage is along one including core wrappage binding part 27 A or multiple regions 29 substantially free of absorbing material form one or more channels 29 '.These channels 29 ' be it is three-dimensional and And it can be used for along its length distributing invasion fluid to the wider region of core.This can provide faster fluid acquisition speed and core The more preferable utilization of absorptive capacity.The deformation of coating such as fibrous layer 54 can also be provided in channel 29 ', and provides in coating Corresponding ditch 29.Being not excluded for absorbent cores may include one or more substantially free of absorbing material but without core wrappage binding part A other regions, but these unglued regions will not usually form slot in wetting.

Upper core cover layer 56 and lower part cover layer 58 can areas along one or more substantially free of absorbing material Domain 29 is continuously attached together, but core wrappage binding part 27 or discontinuous (intermittent), such as a series of Spot bond portion.In general, adhesive can be used for for the top side face of core wrappage being attached to bottom side, but can be by other known Means for attachment such as pressure bonding, ultrasonic wave in conjunction with or hot adhesion or their combination bond.Indicated by following, if Be present in core, then the attachment of the top side face of core wrappage and bottom side can by one or more adhesive materials, specifically one A or multiple auxiliary glue-lines and/or one or more fibrous adhesive material layer provide.Therefore these glue can play fixed suction The dual function received material and be attached together the top side face of core and low side surface.

The following example of the shape and size in the region 29 substantially free of absorbing material is non-limiting.It is general next It says, the tolerance as needed for some manufacturing processes, core wrappage binding part 27 can have the profile identical but smaller with region 29. One or more may be present in the crotch region of product substantially free of the region 29 of material, specifically at least identical as crotch point C Vertical equity on, indicated such as in Fig. 3 by the region 29 that two substantially free of absorbing material longitudinally extend.Absorbent cores 28 It may also include region of the more than two substantially free of absorbing material, for example, at least 3 or at least four or at least five or extremely It is 6 few.Absorbent cores may include the one or more pairs of areas substantially free of absorbing material being arranged symmetrically relative to longitudinal axis 80 Domain.The shorter region of one or more substantially free of absorbing material also is present in the back zone or proparea of such as core, such as See, for example, the attached drawing of WO2012/170778.

Region 29 of the one or more substantially free of absorbing material can generally longitudinally extend, this typically refers to each area Ratio of elongation is horizontally more in the longitudinal direction in domain, and usually extends to that horizontally at least twice is so much (such as exists in the longitudinal direction Measured by after projecting in respective axis).One or more can have projection substantially free of the region 29 of absorbing material Length onto the longitudinal axis 80 of core, the length are at least the 10% of absorbent cores length, specifically 20% to 80%.May have Benefit be at least some of one or more regions 29 or be entirely in core not exclusively or substantially completely horizontal orientation Channel.

Region 29 of the one or more substantially free of absorbing material can be completely machine-direction oriented and be parallel to longitudinal axis, but Or it is curved.Specifically, some or all these regions, being specifically present in these regions in crotch region can be towards vertical To axis 80 be recessed, as in such as Fig. 3 for represented by a pair of channels 29 '.Radius of curvature generally can be at least equal to absorption The average transverse scale of deposited region of material 8 (and is preferably at least 1.5 or at least 2.0 times this average transverse rulers Degree)；And be also straight, but be parallel to the line of longitudinal axis at most 30 ° of (such as 5 °), or such as at most 20 °, or extremely More 10 ° of angles.Radius of curvature can be constant for one or more is substantially free of the region of absorbing material, or It can vary along its length.This may also comprise in one or more regions substantially free of absorbing material wherein with angle, Precondition is to the angle ranging from least 120 °, preferably at least 150 ° between the two parts in channel；And it is any this In a little situations, precondition is that extending longitudinally beyond for region is laterally extended.These regions can also be branch, for example, with crotch region In longitudinal axis superposition rear portion of the central area substantially free of material towards product and/or the preceding part towards product Branch.

In some embodiments, there is no the areas substantially free of absorbing material that the longitudinal axis 80 with core is overlapped Domain.In the presence of in the form of symmetrically one or more pairs of relative to longitudinal axis, one or more areas substantially free of material Domain can be separated from each other in its entire longitudinal size.The smallest spacing can be for example, at least 5mm, or at least 10mm, or extremely Few 16mm.

It in addition to this, is the risk for reducing fluid leakage, one or more regions substantially free of absorbing material can have Any one edge up to absorbing material deposition region 8 is not extended to sharply, and therefore the absorbing material deposition region 8 of core surrounds Or it is entirely included in the absorbing material deposition region 8 of core.In general, one or more regions substantially free of absorbing material Minimum range between the nearest edge of absorbing material deposition region is at least 5mm.

Region of the one or more substantially free of absorbing material along its length can at least partly have an at least 2mm, or The width Wc of at least 3mm or at least 4mm, at most such as 20mm or 16mm or 12mm.One or more is substantially free of absorption material The width Wc in the region of material can be constant in substantially its whole length or can be varied along its length.

When absorbing material absorbs liquid such as urine and starts swelling, the channel 29 ' in absorbent cores is initially formed.It is wicking When receiving more liquid, the recess in absorbent cores formed by channel will become deeper and naked eyes and touch will be become apparent from.Having can The combination of sufficiently strong core wrappage binding part and relatively low amounts super-absorbent polymer particles can be generated, so that channel keeps permanent Until absorbing material is fully saturated.On the other hand, in some cases, core wrappage binding part can also be when core substantially loads Limit the swelling of absorbing material.

Initially, one or more core wrappage binding parts be designed to closure and increase neighbouring one or more core packets Wrap up in the pressure in the region of object binding part.Under certain conditions, core wrappage binding part (27) also is designed to work as and be exposed to It is opened in a controlled manner when a large amount of fluids.

Test method

·The screening of quality measurement average particle size (mAvPS) is tested:

All tests carry out under 23 DEG C ± 2 DEG C and 45% ± 10% relative humidity.

The corresponding precursor super-absorbent polymer particles of 10g (± 0.1g is weighed into at least precision of 0.01g) or surpassing for agglomeration The representative sample of absorbent polymer particles by the sieve of diameter about 20cm (such as purchased from Retsch GmbH, Haan, Germany；DIN/ISO 3310-1) screening.Use the sieve with following mesh size (by sequence from the top to the bottom) It stacks: 1600 μm, 1400 μm, 1000 μm, 850 μm, 710 μm, 600 μm, 500 μm, 425 μm, 300 μm, 212 μm, 150 μm, 106 μm, 63 μm, 45 μm and screen frame (unit) (being considered as equal to 1 μm herein).The weight for recording each empty sieve, until the precision of 0.01g.

10g sample is loaded into top sieve (i.e. 1600 μm) and at 1mm/`g ' via screening machine (" AS 00control` G ' " is purchased from Retsch GmbH, Haan, Germany) screening 3 minutes.The weight of each sieve after record screening, until 0.01g Precision.For each sieve mesh, the difference between the sieve of load and empty sieve provides the particle weight of every sieve mesh.

If the difference between the sieve and empty sieve that load is negative value, but be greater than negative 0.02g (since weighing precision is 0.01g, This may occur), then minus tolerance is construed to 0.

If the difference between the sieve and empty sieve that load is negative value and is less than negative 0.02g (for example, negative 0.5g), sieve is abandoned The result of point test is laid equal stress on secondary screening point test.

According to sieve mesh, sieve label Di is for example the part for having D500 for the measurer of m500 for 500 μm of acquisitions of sieve, Wherein D500=500 μm.

The quality average particle size (mAvPS) of this paper calculates are as follows:

At the top of i=_ arrive _ bottom

Example calculation:

Sieve size [μm]	Residual fraction [g] on sieve	Percentage
			1600	0.00	0.0%
1400	0.00	0.0%
			1000	0.00	0.0%
850	0.30	3.0%
			710	0.70	7.0%
600	1.30	13.0%
			500	3.80	38.0%
425	2.40	24.0%
			300	0.50	5.0%
212	0.70	7.0%
			150	0.30	3.0%
106	0.00	0.0%
			63	0.00	0.0%
45	0.00	0.0%
			1	0.00	0.0%
It amounts to	10.00	100.0%

Table 1

In this example, mAvPS is 486 μm.

In order to simplify screening program, in the particle for not expecting a certain size (for example, if carrying out sample in sample preparation Pre-screening) in the case where, the sieve for reducing and stacking can be used.

For example, just following sieve can be used to stack with the pre-screening sample of 150 μm of pre-screening upper dimension bounds: 300 μm, 212 μm, 150 μm, 106 μm, 63 μm, 45 μm and screen frame (unit) (being considered as equal to 1 μm herein).

Note: in the case where being stacked using reduced sieve, top (or bottom) sieve should load total no more than 5 weight % Sample.If useful load > 5 weight %, need to include adding the sieve of appropriate size, and need to repeat to sieve to survey in stacking Examination.

For example, following sieve can be used to stack: 1600 μ for the pre-screening sample with 850 μm of pre-screening lower size limits M, 1400 μm, 1000 μm, 850 μm, 710 μm, 600 μm, 500 μm and screen frame (unit) (being considered as equal to 1 μm herein).

·Urine permeability measures (UPM) test method

Laboratory condition:

The test must be under the standard conditions of 23 DEG C of ± 2 DEG C of temperature and 45% ± 10% relative humidity in climate chamber Middle progress.

Urine permeability measuring system

The permeability of this method measurement hydrogel glue-line 1318.Apparatus for the method is described as follows.This method with SFC (salt flows conductivity or saline flow conductivity) test method of the prior art is closely related.

Fig. 6 shows permeability measuring system 1000, enters equipped with permanent hydrostatic head reservoir 1014, for air Be open end pipe 1010, the mouth 1012 for refilling, experimental stand 1016, with the flexible pipe with Tygon pipe nozzle 1044 1045 transfer tube 1018, cock 1020, cover plate 1047 and support ring 1040, receive container 1024, balance 1026 and piston/ Cylinder sub-assembly 1028.

Fig. 7 is shown including metal weight 1112, piston shaft 1114, piston head 1118, capping 1116 and cylinder 1120 Piston/cylinder sub-assembly 1028.Cylinder 1120 by transparent polycarbonate (such as) be made and have 6.00cm's Internal diameter p (area=28.27cm²), wherein inner cylindrical wall 1150 is smooth.The bottom 1148 of cylinder 1120 is covered with stainless steel Screen cloth (ISO9044 material 1.4401, mesh size 0.038mm, mesh wire diameter 0.025mm) (not shown), is being attached to circle Biaxial stretching is to tensioned state before on the bottom 1148 of cylinder 1120.Piston shaft 1114 by transparent polycarbonate (such as) it is made and has the total length q of about 127mm.The middle section 1126 of piston shaft 1114 have 22.15 (± 0.02) the diameter r of mm.The top 1128 of piston shaft 1114 has the diameter s of 15.8mm, to form shoulder 1124.Piston shaft 1114 lower part 1146 has about 5/8 inch (15.9mm) of diameter t, and is screwed to be firmly screwed in piston head 1118 (referring to Fig. 8) in heart hole 1218.Piston head 1118 is perforated, by transparent polycarbonate (such as) be made, and And also it is obscured with stainless steel mesh cloth (9044 material 1.4401 of ISO, mesh size 0.038mm, the mesh wire diameter of stretching 0.025mm) (not shown).Counterweight 1112 is stainless steel, has central bore 1130, slides into the top of piston shaft 1114 On 1128 and rest on shoulder 1124.The combined wt of piston head 1118, piston shaft 1114 and counterweight 1112 is 596g (± 6g), It is equivalent to the 0.30psi on 1120 inner region of cylinder.The downward drilling blind hole of central axis 1132 along piston shaft 1114 can be passed through Combined wt is adjusted to remove material and/or provide cavity to increase counterweight.In the center there is first for cylinder capping 1116 Capping opening 1134 is for perpendicular alignmnet piston shaft 1114, and by proximal edge 1138 there is the second capping opening 1136 to be used for will Fluid introduces cylinder 1120 by permanent hydrostatic head reservoir 1014.

The first linear cue mark (not shown) is marked along the upper surface 1152 of counterweight 1112 is radial, described first is linear Central axis 1132 of the cue mark transverse to piston shaft 1114.Phase is marked along the top surface 1160 of piston shaft 1114 is radial The linear cue mark (not shown) of second answered, central axis of the second linear cue mark transverse to piston shaft 1114 1132.Corresponding third linear cue mark (not shown) is marked along 1114 middle part 1126 of piston shaft, the third linear refers to The central axis 1132 for being parallel to piston shaft 1114 is remembered in indicating.It is marked accordingly along the upper surface 1140 of cylinder capping 1116 is radial The 4th linear cue mark (not shown), central axis 1132 of the 4th linear cue mark transverse to piston shaft 1114. In addition, marking the corresponding 5th linear cue mark (not shown) along the antelabium 1154 of cylinder capping 1116, the 5th is linear Cue mark is parallel to the central axis 1132 of piston shaft 1114.The corresponding 6th linear instruction is marked along outer cylindrical wall 1142 (not shown) is marked, the 6th linear cue mark is parallel to the central axis 1132 of piston shaft 1114.Make first, second, Three, the four, the 5th and the 6th linear cue mark is aligned so that counterweight 1112, piston shaft 1114, cylinder capping 1116 and circle Cylinder 1120 is relocated in each measurement with identical orientation relative to each other.

1120 specification details of cylinder are as follows:

The outer diameter u:70.35mm (± 0.05mm) of cylinder 1120

The internal diameter p:60.0mm (± 0.05mm) of cylinder 1120

Height ν: 60.5mm of cylinder 1120.Cylinder heights must be not less than 55.0mm！

Cylinder covers 1116 specification details are as follows:

The outer diameter w:76.05mm (± 0.05mm) of cylinder capping 1116

The internal diameter x:70.5mm (± 0.05mm) of cylinder capping 1116

The thickness y:12.7mm of cylinder capping 1116 including antelabium 1154

The thickness z:6.35mm of roller capping 1116 when no antelabium 1154

The diameter a:22.25mm (± 0.02mm) of first capping opening 1134

The diameter b:12.7mm (± 0.1mm) of second capping opening 1136

The distance between the center at the center of the first capping opening 1134 and the second capping opening 1136: 23.5mm

1112 specification details of counterweight are as follows:

Outer diameter c:50.0mm

The diameter d:16.0mm of central bore 1130

Height e:39.0mm

1118 specification details of piston head are as follows:

Diameter f:59.7mm (± 0.05mm)

Height g:16.5mm.Piston grease head highness must not drop below 15.0mm.

Exit orifice 1214 (in total 14) has the diameter h of 9.30 (± 0.25) mm, and exit orifice 1214 is equally spaced, wherein in Heart 23.9mm away from the center of centre bore 1218.

Inner hole 1216 (in total 7) has the diameter i of 9.30 (± 0.25) mm, and inner hole 1216 is equally spaced, wherein in Heart 13.4mm away from the center of centre bore 1218.

Centre bore 1218 has about 5/8 inch (15.9mm) of diameter j, and is screwed to accommodate the lower part of piston shaft 1114 1146。

Before the use, it should check whether the stainless steel mesh (not shown) of piston head 1118 and cylinder 1120 blocks, breaks Hole or excessive tensile, it is replaceable if necessary.The UPM of the exportable mistake of urine permeability measuring device with impaired sieve is tied Fruit, and not used centainly before sieve replacement.

On cylinder 1120 above the sieve (not shown) on the bottom 1148 for being attached to cylinder 1120 5.00cm (± 5.00cm label 1156 is marked at height k 0.05cm).The fluid content to be kept during this labeled analysis.Keep it is correct and Constant fluid content (fluid pressure) is very crucial for measuring accuracy.

Constant static pressure head reservoir 1014 is used to salting liquid 1032 being transmitted to cylinder 1120, and keeps salting liquid 1032 Level is above the sieve (not shown) on the bottom 1148 for being attached to cylinder 1120 at the height k of 5.00cm.Position air inlet pipe 1010 bottom 1034, to keep 1032 level of salting liquid in cylinder 1120 in required 5.00cm height during measurement At k, i.e., when positioned at the cover plate 1047 and support ring 1040 for receiving 1024 top of container, (its round inner opening has cylinder 1120 Diameter not less than 64mm) on when, the 5.00cm label 1156 on the bottom 1034 of air inlet pipe 1010 and cylinder 1120 is located at big It causes in same plane 1038.

Cover plate 1047 and support ring 1040 are that method " test side K (t) is used for as described in 2 535 027 A1 of EP Component used in the equipment of method (dynamic effective permeability and absorption dynamics measure test method) ", and be referred to asOr " time dependence osmolarity tester ", equipment are compiled Number 03-080578, and it is commercially available be obtained from BRAUN GmbH, Frankfurter Str.145,61476Kronberg, Germany.According to requiring, detailed technical drawing can also be provided.

Air inlet pipe 1010 and being suitably highly aligned for the 5.00cm label 1156 on cylinder 1120 are very crucial for analyzing.It closes Suitable reservoir 1014 is made of wide-mouth bottle 1030, which includes: the L shape transfer tube for the horizontal alignment of fluid transmission 1018, it is connected to flexible pipe 1045 (for example, Tygon pipe that nozzle and reservoir exit port can be connected) and Tygon pipe nozzle 1044 (internal diameter is at least 6.0mm, and length is about 5.0cm)；For allowing air to be in permanent hydrostatic head reservoir 1014 Vertically oriented distal opening pipe 1010 at fixed height；And the mouth for refilling permanent hydrostatic head reservoir 1014 1012.Pipe 1010 has about 12mm, but is not less than the internal diameter of 10.5mm.Close to the bottom of constant static pressure head reservoir 1014 The transfer tube 1018 of 1042 positioning includes the cock 1020 for starting/stopping the transmission of salting liquid 1032.Customization transmission flexible pipe The size (for example, overall diameter 10mm) of 1045 outlet 1044 covers opening 1136 to pass through second in cylinder capping 1116, Its end, which is located under the surface of the salting liquid 1032 of cylinder 1120, (reaches 5.00cm in cylinder 1120 in salting liquid 1032 After height).Air inlet pipe 1010 is held in place with O-ring lining ring 1049.Permanent hydrostatic head reservoir 1014 can be determined Position is on laboratory bench 1016, and the height relative to cylinder 1120 is at proper height.Customize permanent hydrostatic head reservoir 1014 Size of components keep the height so as to Fast Filling cylinder 1120 to desired height (that is, hydrostatic head) and during entire measurement Degree.Permanent hydrostatic head reservoir 1014 allows for transmitting salting liquid 1032 at least 10 minutes with the flow of at least 2.6g/s.

Piston/cylinder sub-assembly 1028 is positioned in the support ring 1040 in cover plate 1047 or suitable optionally rigidity On bracket.It is collected in and connects by the inclusion of the salting liquid 1032 of the piston/cylinder sub-assembly 1028 of the hydrogel layer 1318 of swelling In receptacle 1024, which is located in the lower section (but not contacting) of piston/cylinder sub-assembly 1028.

Container 1024 will be received to be placed on the balance 1026 for being accurate at least 0.001g.The numeral output of balance 1026 is connected It is connected in the data collection system 1048 of computer disposal.

Reagent prepares (not shown)

Jayco synthetic urine solution (JSU) 1312 (referring to Fig. 9), which is used as, is swollen phase (referring to following UPM program), and 0.118M Sodium chloride (NaCl) solution 1032 is used as mobile phase (referring to following UPM program).Prepare below be reference standard 1 liter of volume. If preparation is different from 1 liter of volume, therefore all amounts weigh in proportion.

JSU: with the volumetric flask of distilled water filling 1L to the 80% of its volume, and magnetic stirring bar is placed in volumetric flask. Weigh the dry ingredient of following amount (being accurate to ± 0.01g) respectively using assay balance pan paper or beaker, and by they with Same sequence enumerated below is quantitatively adding in volumetric flask.The agitating solution on agitator disk appropriate is until all solids are molten Solution takes out stirring rod, and with the volume of distilled water dilute solution to 1L.It is placed again into stirring rod, and is in addition stirred in stirring rod Mix solution a few minutes.

Prepare the salt dosage of 1 liter of Jayco synthetic urine solution:

Potassium chloride (KCl) 2.00g

Sodium sulphate (Na2SO4) 2.00g

Ammonium dihydrogen phosphate (NH4H2PO4) 0.85g

Diammonium hydrogen phosphate ((NH4) 2HPO4) 0.15g

Calcium chloride (CaCl2) 0.19g-[or calcium chloride hydrate (CaCl22H2O) 0.25g]

Magnesium chloride (MgCl2) 0.23g-[or hydrated magnesium chloride (MgCl26H2O) 0.50g]

In order to make preparation faster, by potassium chloride, sodium sulphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and magnesium chloride (or hydration chlorine Change magnesium) it mixes and in 80% distilled water that is dissolved in 1L volumetric flask.Calcium chloride (or calcium chloride hydrate) is dissolved separately in greatly In (such as in glass beaker) about 50ml distilled water, and calcium chloride solution is turned after other salt are dissolved completely in wherein It moves on in 1L volumetric flask.Then, addition distilled water is to 1L (1000ml ± 0.4ml), and solution is stirred for a few minutes. Jayco synthetic urine solution can store 10 days in clean plastic containers.If solution becomes cloudy, which should not be reused.

Sodium chloride (NaCl) solution of 0.118M: the sodium chloride of 0.118M is used as salting liquid 1032.Using pan paper or Beaker weighs 6.90g (± 0.01g) sodium chloride and is quantitatively transferred to it in volumetric flask (1000ml ± 0.4ml) of 1L；And With distilled water by volumetric flask constant volume.Be added stirring rod and on agitator disk agitating solution until all solids dissolve.

The conductivity of prepared Jayco solution must be and prepared in the range of about 7.48-7.72mS/cm 0.118M sodium chloride (NaCl) solution conductivity in the range of about 12.34-12.66mS/cm (for example, by following Apparatus measures: 70 instrument of COND without battery, #50010522, equipped with the Cell for being purchased from xs instruments VPT51-01 C=0.1；Or LF 320/Set, #300243, equipped with the TetraCon 325 for being purchased from WTW；Or COND 330i, #02420059, equipped with the TetraCon 325 for being purchased from WTW).The surface tension of every kind of solution must be in 71-75mN/m In the range of (for example, pass through with Pt plate purchased from Kruess tensometer K100 measure).

Test prepares

Utilize solid reference cylinder counterweight (not shown) (50mm diameter；128mm height), calliper (not shown) (is surveyed Range 25mm is measured, 0.01mm, piston pressure maximum 50g are accurate to；For example, Mitutoyo Digimatic Height Gage) It is set as reading zero.This is carried out on the smooth horizontal table (not shown) of at least about 11.5cm × 15cm easy to operately. Piston/cylinder sub-assembly 1028 without super-absorbent polymer particles is located in below calliper (not shown), and records reading L1 is accurate to 0.01mm.

Permanent hydrostatic head reservoir 1014 is filled with salting liquid 1032.The bottom 1034 of air inlet pipe 1010 is positioned, to survey Keep the top (not shown) of liquid meniscus (not shown) in cylinder 1120 at 5.00cm label 1156 during amount.Air inlet pipe The 1010 appropriate height alignment at the 5.00cm label 1156 on cylinder 1120 is very crucial for analyzing.

Container 1024 will be received to be placed on balance 1026, and the numeral output of balance 1026 is connected to computer disposal Data collection system 1048.Cover plate 1047 with support ring 1040, which is located in, receives 1024 top of container.

UPM program

1.5g (± 0.05g) super-absorbent polymer particles are weighed to suitable weighing paper using assay balance or are weighed auxiliary On assistant engineer's tool.The water content of super-absorbent polymer particles is according to the aqueous weight testing method NWSP 230.0.R2 (15) of Edana or leads to Cross moisture analyser (purchased from the HX204 of Mettler Toledo, 130 DEG C of drying temperature, starting superabsorbents weight 3.0g (± 0.5g), stopping criterion 1mg/140s) it measures.If the water content of super-absorbent polymer particles is greater than 3 weight %, will surpass The absorbent polymer particles dry 3h or dry 2h to < 3 weight % for example in 120 DEG C of baking oven for example in 105 DEG C of baking oven Water content.If moisture content is greater than 5 weight %, by the super-absorbent polymer particles of agglomeration for example in 105 DEG C of baking oven The middle dry 3h or dry 2h for example in 120 DEG C of baking oven.

Empty cylinder 1120 is placed on 1046 (not shown) of horizontal table, and super-absorbent polymer particles are quantified and are turned It moves on in cylinder 1120.Super-absorbent polymer particles are evenly dispersed in the sieve for being attached to the bottom 1148 of cylinder 1120 On (not shown), at the same for example by means of (manually or electrically) turntable (for example, purchased from Schuett petriturn-E or Petriturn-M) rotor 1120.Particle is uniform on the sieve (not shown) for the bottom 1148 for being attached to cylinder 1120 Be distributed it is critically important, to obtain highest precision result.It has been evenly distributed in super-absorbent polymer particles and has been attached to cylinder 1120 Bottom 1148 sieve (not shown) on after, particle cannot be centainly attached on inner cylindrical wall 1150.It is inserted into piston shaft 1114 By the first capping opening 1134, wherein the antelabium 1154 of capping 1116 faces piston head 1118.Carefully by piston head 1118 It is inserted into cylinder 1120 to several centimetres of depth.Then capping 1116 is placed into the top edge 1144 of cylinder 1120, together When carefully keep piston head 1118 far from super-absorbent polymer particles.Counterweight 1112 is placed in the top 1128 of piston shaft 1114 On, so that it is rested on shoulder 1124, so that the first linear cue mark is aligned with the second linear cue mark.Then careful rotation Turn capping 1116 and piston shaft 1126, to arrange third linear cue mark, the 4th linear cue mark, the 5th linear instruction They, are then aligned by label and the 6th linear cue mark with the first linear cue mark and the second linear cue mark.So Reduce piston head 1118 (passing through piston shaft 1114) gently afterwards to rest on dry super-absorbent polymer particles.Capping 1116 Appropriate location prevent the bonding of counterweight on hydrogel layer 1318 and ensure to evenly distribute.

It is swollen phase:

To have " thick " or " additional thick " hole (such as Chemglass Inc.#CG 201-51, coarse porosity；Or for example have Have the Robu 1680 of porosity 0) at least 8cm diameter (such as 8-9cm diameter) and at least (such as 5-7mm is thick for 5.0mm thickness Degree) sintering pan 1310 be placed in wide flat culture dish 1314, and by the way that JSU 1312 is poured into sintering pan 1310 JSU 1312 is added on center, until JSU 1312 reaches the top surface 1316 of sintering pan 1310.The height of JSU is centainly not It to be more than the height of sintering pan 1310.It is important to avoid that any air or bubble be embedded in sintering pan 1310 or below.

Entire piston/cylinder sub-assembly 1028 is promoted on the sintering pan 1310 being placed in culture dish 1314.Derived from training The JSU 1312 of ware 1314 is supported to absorb by sintering pan 1310, and by super-absorbent polymer particles (not shown) to form water-setting Glue-line 1318.Obtainable JSU 1312 should be sufficiently used for all swelling phases in culture dish 1314.If desired, can be in water More JSU 1312 are added in culture dish 1314 during conjunction, to keep the horizontal top for being in sintering pan 1310 JSU 1312 At portion surface 1316.After 60 minutes periods, piston/cylinder sub-assembly 1028 is removed from sintering pan 1310, is paid attention to Ensure that hydrogel layer 1318 does not lose JSU 1312 or sucking air in this step.Piston/cylinder sub-assembly 1028 is placed in Under calliper (not shown) and reading L2 is recorded, is accurate to 0.01mm.If reading changes over time, initial value is only recorded. The thickness L0 that hydrogel layer 1318 is determined by L2-L1, is accurate to 0.1mm.

Piston/cylinder sub-assembly 1028 is transferred in the support ring 1040 in cover plate 1047.Permanent hydrostatic head is stored Device 1014 is located so that transfer tube nozzle 1044 is placed by the second capping opening 1136.Start to measure in the following order:

A) cock 1020 of permanent hydrostatic head reservoir 1014 is opened to allow salting liquid 1032 to reach on cylinder 1120 5.00cm label 1156.1032 content of salting liquid should obtain in 10 seconds for opening cock 1020.

B) once the salting liquid 1032 of 5.00cm is obtained, with regard to log-on data capture program.

By the computer 1048 being attached on balance 1026, the salt of hydrogel layer 1318 was passed through with 20 seconds interval records The quality g (unit g, be accurate to 0.001g) of solution 1032, time are 10 minutes.At the end of 10 minutes, permanent static pressure is closed Cock 1020 on head reservoir 1014.

The data terminated from 60 seconds to experiment are used in UPM calculating.The data acquired before 60 seconds are not included in calculating In.

For 20 second period (time t each of after initial 60 seconds of experiment_(i-1)To t_i), phase is calculated according to the following formula Answer flow Fs_(t)(unit g/s) and corresponding center time point t_(1/2)t(unit s):

Draw each time interval (t_(i-1)To t_i) flow Fs_(t)Relative to time interval (t_(i-1)To t_i) time in Point t_(1/2)tCurve.Intercept is calculated as F (t=0).

The calculating of intercept:

Intercept is for example calculated as follows by best-fit regression line: the equation a of tropic intercept are as follows:

A=y_AVG-b·x_AVG (III)

Wherein slope b is calculated are as follows:

And wherein x_AVGAnd y_AVGRespectively known _ sample average average value of x and the sample average average value of known _ y.

The calculating of urine permeability measurement Q:

Intercept Fs (t=0) for calculating Q according to the following formula:

Wherein flow Fs (t=0) is provided with g/s, L₀For the original depth of hydrogel layer 1318, unit cm, ρ are that salt is molten The density of liquid 1032, unit g/cm³(for example, being at room temperature 1.003g/cm³).A (carrying out self-ascending type) is hydrogel layer 1318 Area, unit cm²(for example, 28.27cm²), Δ P is fluid pressure, unit dyn/cm²(for example, 4920dyn/ cm²), and urine permeability measurement Q is with cm³S/g is unit.The average value measured three times should be recorded.

Table 2

·Free swell rate (FSR) test method

This method measures super-absorbent polymer particles (super-absorbent polymer particles of agglomeration such as of the invention), especially (NaCl of 0.9 mass % is containing water-soluble in 0.9% saline solution for the polyacrylate that polymer hydrogel particles are such as crosslinked Liquid) in swelling rate.Measuring principle is the fluid for making super-absorbent polymer particles absorb known quantity, and measures and absorb fluid institute The time of cost.Then result is expressed as every gram of material absorption fluid grams per second.All tests at 23 DEG C ± 2 DEG C and It is carried out under 45% ± 10% relative humidity.

In the case where the moisture content of the sample of super-absorbent polymer particles is greater than 5 weight %, by sample for example 105 DEG C baking oven in dry 3 hours or in 120 DEG C of baking oven it is 20 minutes 2 hours dry.Drying temperature must not be excellent higher than 180 DEG C Selection of land is not higher than 150 DEG C.

By the test sample weighing (being accurate to 0.001g) of about 1g (+/- 0.1g) into the beaker of 25ml, which has The internal diameter of 32mm to 34mm and the height of 50mm.Material is uniformly spread on bottom.The salt water of 20g 0.9% is weighed to In the beaker of (being accurate to +/- 0.01g) 50ml, and then carefully rapidly it is poured into the beaker comprising test material. Start timer immediately in fluid contact material.Beaker is not moved or is stirred during swelling.

When the last part for being undisturbed fluid is touched by swellable particles, stops timer and record the time, be accurate to Second (or if appropriate more accurately).In order to increase the reproducibility of end point determination, liquid surface can be illuminated with small lamp and The unused lamp heating surface.The beaker of salt water is filled to measure the liquid actually drawn before weighing again, be accurate to ± In 0.1g.

As shown by the following formula, by by the quality of absorbed liquid divided by super-absorbent polymer particles quality again divided by Time is calculated free swell rate and is indicated with " g/g/s ".

It calculates free swell rate and is averaged to obtain the FSR value as unit of g/g/s, accurate record to 0.01g/ g/s。