CN88100333A - Absorbent composite - Google Patents
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- CN88100333A CN88100333A CN88100333.6A CN88100333A CN88100333A CN 88100333 A CN88100333 A CN 88100333A CN 88100333 A CN88100333 A CN 88100333A CN 88100333 A CN88100333 A CN 88100333A
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Abstract
A kind of composite material of imbibition, by water absorbent polymer (a), water-insoluble inorganic materials (b) and water-insoluble hydrophilic fibers material (c) are pressed (a): (b): () formed by 100: 5～1200: 5～1200 weight ratio.It is preparation sanitary napkin and the extremely useful absorbent composition of medical liner.
Description
The present invention relates to absorbent composite and relate to the production method of the imbibition goods that contain this type of matrix material.This type of matrix material is exceedingly useful for the absorbent products that preparation can absorb liquid and reservation absorption liquid.As the sanitary napkin in health and the medical treatment product, disposable diaper is used for the preservation agent and the vegetables moisture preservatives of agricultural, forestry aspect, it also can be used as sanitary pads, as the liner that newborn woman breast-feeds, child's mattress, incontinence patient, hemorrhoid patient's mattress and operation liner.
In recent years, a kind of material that is called as water absorbent polymer that can absorb own wt tens to hundred times water has appearred.It is used to do the medical treatment product such as coating of sanitary product such as sanitary towel, paper nappy and contact lens, operation stitching part.Aspect the separation and purifying of material, can be used as the carrier of liquid chromatography, aspect forestry, agricultural and civil engineering work, then can be used as moisture preservatives and water-absorbing material.
The example of being familiar with in above-mentioned water-absorbing polymer has crosslinked polyacrylic ester, starch-acrylate graft copolymer, the vinyl acetate-acrylate multipolymer of the Mierocrystalline cellulose of hydrolysis-acrylonitrile grafting polymkeric substance and hydrolysis.These water-absorbing polymers are splendid for the receptivity of low-viscosity (mobile) liquid such as water and urine, and absorb rapidly, and absorbed dose is big.In addition, existing people has proposed the various recommendation on improvements to this material.
On the other hand, can absorb the absorbency polymkeric substance of high viscosity liquid such as blood for preparation, some of the recommendations propose material is become porous (seeing Japanese patent application publication No. 71728/80 and 8711/84), can add water-soluble organic salt and/or inorganic salt and (see the PCT patent application N of published Japan translation
o501107/1983), reaches and hydrophilic fibre such as paper pulp blend (seeing Japanese patent application publication No. 86657/1984).But aforesaid method is not received satisfied effect.
Therefore, urgent hope can have a kind of liquid sucting copolymer of absorptive character excellence, that is: capacity is big, and absorption speed is fast, and absorbing power is strong, not only absorbs low-viscosity (mobile) liquid, and can absorb the liquid sucting copolymer of high viscosity liquid.
In these cases, in order to prepare heavy body, speed is fast, absorbing power is strong, not only absorb slurries in low-viscosity (mobile) liquid such as water, urine and the body, and can absorb the water-absorbing polymer of high viscosity liquid such as blood, body fluid and ight soil etc., inventors of the present invention have carried out research extensively and profoundly, found that in absorbent polymer, to add and fixing a certain amount of water-insoluble inorganic materials and water-insoluble hydrophilic fibers material, can obtain unprecedented excellent absorbent composites.This invention work has been finished in this discovery.
Contain (a) water-absorbing polymer in the composite material of imbibition of the present invention, (b) water-insoluble inorganic materials and (c) water-insoluble hydrophilic fibers material, the weight ratio of its (a) and (b), (c) is in 100: 5～1200: 5～1200 scopes.
Its advantage is that its bulk specific gravity is 0.03～0.7 gram/cubic centimetre.Polymkeric substance can be polymer or its cross-linking products of water-soluble ethylenically unsaturated monomers, is major ingredient with vinylformic acid or acrylate.Inorganic materials (b) can be selected from aluminum oxide, silicon oxide, zeolite, polynite family clay and kaolin group's clay.Filamentary material (c) is natural or the synthetic Mierocrystalline cellulose.
The invention provides absorbency goods by above-mentioned absorbent composite preparation.
The present invention also provides the technology of producing this type of composite material of imbibition.This technology is in the presence of the water of 70～3000 parts (weight) (is benchmark with 100 parts (a)), mixes (a) and (b) and (c).The step that also can comprise drying composite in this technology.
Can be applicable to water-absorbing polymer of the present invention in general can be any absorptive polymkeric substance that has.As polyacrylic ester and cross-linking products thereof, polyethylene oxide, Polyvinylpyrolidone (PVP), crosslinked sulphonated polystyrene and polyvinylpyridine, saponified starch-poly-(methyl) acrylonitrile graft copolymer, the graft copolymer (and cross-linking products) of starch-poly-(methyl) vinylformic acid (and salt), the reaction product of polyvinyl alcohol and maleic anhydride (and salt), and the hydrolysate of starch-poly-(methyl) acrylate graft copolymers.In addition, also can use polyvinyl alcohol sulphonate, polyvinyl alcohol-acrylic acid graft copolymer etc.The better polymkeric substance of the water-soluble ethylenically unsaturated monomers mainly formed by vinylformic acid or acrylate of polymkeric substance or their cross-linking products.Then can select arbitrarily as for their method of preparation.
These polymkeric substance can be used in combination by wherein two or more.Water-absorbing polymer calculates the water that every gram can absorb 20 milliliters by its weight, and is powder, grain, piece or sheet.Matrix material of the present invention can be with the polymer manufacture of above-mentioned any shape.When used polymkeric substance is a powdery or when granular, preferably its particle diameter is 10～3000 microns, better at 15～1000 microns.
Employed inorganic materials must be water insoluble basically among the present invention, as long as meet this basic demand, any material all can use.Inorganic materials used among the present invention has aluminum oxide, silicon oxide, titanium dioxide, talcum, zirconium white, calcium phosphate, barium phosphate, calcium sulfate, clay, silicic acid, diatomite, bentonite, gac, zeolite, kaolin, acid clay, activated clay, vermiculite, and other metal oxide.Aluminum oxide wherein, silicon oxide, zeolite, polynite family clay (bentonite), and kaolin group's clay (kaolin) is better.The particle diameter of water-insoluble inorganic materials has no particular limits.But its particle diameter is preferably 1500 microns or littler, 500 microns or then better less than 500 microns effects.
The example that can be used as water-insoluble hydrophilic fibers material among the present invention comprises the water-insoluble filamentary material with wetting properties and liquid guide flow characteristic, as cellulose powder, and paper pulp, regenerated fiber, vinylon, cotton, wool and cellulose acetate.Natural and artificial cellulose's powder, paper pulp, the result of use of regenerated fiber is especially good.In addition, in order to give some functions of material such as melting immobilization, hydrophobic fiber material such as polyester, polyethylene, polypropylene, polyvinyl chloride, acrylic acid or the like and nylon can use with water-insoluble hydrophilic fibers material mixing.Though only otherwise destroy the wetting ability of matrix material, the hydrophobic fiber material can use in very wide proportional range according to its purposes, and the content of water-insoluble hydrophilic high mol generally should be 60%(weight) or it is higher, preferably 80% or the highest.Filamentary material can be macrofiber, staple fibre or fine powder.Staple length is generally wanted 50 millimeters or short, best 40 millimeters or less than 40 millimeters.
The ratio that water-absorbing polymer, water-insoluble inorganic materials and water-insoluble hydrophilic fibers material use is to be benchmark with 100 parts of water-absorbing polymers, water-insoluble inorganic materials and water-insoluble hydrophilic fibers material correspondingly respectively are 5～1200 parts and 5～1200 parts (weight), better ratio should be 10～800 parts and 10～1000 parts, preferably 20～500 parts and 20～800 parts mutually.Lack any composition in the above-mentioned prescription and all can not get effect among the present invention, therefore, inconsistent with the present invention.When the amount ratio of water-insoluble inorganic materials during less than 5 parts, the absorption rate and the receptivity of this composite material of imbibition are all very little.On the other hand, when its consumption surpassed 1200 parts, not only absorptive capacity reduced, and the water-insoluble inorganic materials can not be fixed on the polymkeric substance, therefore can not reach purpose of the present invention.When the consumption of water-insoluble hydrophilic fibers material during less than 5 parts, the liquid guide flow of composite material of imbibition and absorption speed are all less, and when its consumption surpassed 1200 parts, the absorptive capacity of this material was less, and this can not reach purpose of the present invention.The ratio of water-insoluble inorganic materials and water-insoluble hydrophilic fibers material can at random be regulated in above-mentioned scope according to its kind and purposes that will absorb liquid.
Though composite material of imbibition can prepare with ready-made method according to the present invention, following method is better.
Specifically, composite material of imbibition is to prepare by the method that adds water-insoluble inorganic materials and water-insoluble hydrophilic fibers material in the water-soluble polymers of abundant solvent swelling state.An example of this method is to drop into swollen polymkeric substance, water-insoluble inorganic materials and water-insoluble hydrophilic fibers material in kneading-mixing machine, and it is mixed and dry products therefrom.Another example is to add water-absorbing polymer, water, water-insoluble inorganic materials and water-insoluble hydrophilic fibers material continuously while stirring in organic solvent, and the gained mixture is filtered and dry cake.Also having an example is that water-insoluble inorganic materials and water are mixed in the spiral rotary blender, to wherein adding water-absorbing polymer and water-insoluble hydrophilic fibers material continuously, makes it mix desciccate then.The oriented water-soluble ethylenically unsaturated monomers of other method or contain and add water-insoluble inorganic materials and water-insoluble hydrophilic fibers material in the water-soluble ethylenically unsaturated monomers of crosslinkable groups makes monomer polymerization, and desciccate.The method for preparing composite material of imbibition is not limited only to aforesaid method.If necessary, the composite material of imbibition that drying can be crossed carries out pulverization process.
In addition, the invention provides the novel method of the composite material of imbibition of effective production.At first add about 20 ml waters or higher ratio adds entry in water-absorbing polymer with every gram polymkeric substance, add water-insoluble inorganic materials and water-insoluble hydrophilic fibers material after the water absorbent polymer swelling and with its mixing, thereby make water-insoluble inorganic materials and water-insoluble hydrophilic fibers material deposition or be bonded on the swollen water absorbent polymer.If necessary, with the product drying.
Not only can liquid form add water, can also steam spray or the mode of injection add water.Any one aforesaid method all can use effectively.
Water-absorbing polymer, there is no particular limitation for the order of addition(of ingredients) of water-insoluble inorganic materials, water-insoluble hydrophilic fibers material and water and method.But it is reasonable that two kinds of methods are arranged.The first adds water-insoluble inorganic materials and water-soluble hydrophilic fibers material in the swollen polymer together.It two is that water-insoluble hydrophilic fibers material is added in the kneading mixture of water-absorbing polymer, water and water-insoluble inorganic materials.These two kinds of methods can be given full play to various raw-material functions.
The method of mixing above-mentioned various single materials also has no particular limits.Mainly contain three kinds of methods.The first adds swollen polymkeric substance, water-insoluble inorganic materials, water-insoluble hydrophilic fibers material and with its mixing, desciccate in the mixing vessel of rotation or fixed mixing vessel.It two is that the water-insoluble inorganic materials is mixed with water, to wherein adding water-absorbing polymer and water-insoluble hydrophilic fibers material continuously, it is mixed and desciccate.Its three be under agitation with the immiscible basically organic solvent of water in add continuously water-absorbing polymer, water, water-insoluble inorganic materials and water-insoluble hydrophilic fibers material, the gained mixture is filtered and dry cake.
In order to be that medium is transformed into matrix material with water with above-mentioned water-absorbing polymer, water-insoluble inorganic materials, water-insoluble hydrophilic fibers material, with 100 parts of (weight) water absorbent polymers is benchmark, the used in amounts of water will be preferably in 200～1500 parts at 70～3000 parts.When the consumption of water during less than 70 parts, water-insoluble inorganic materials and water-insoluble hydrophilic fibers material are to the deposition of water absorbent polymer or bonding then incomplete, and the matrix material of making thus can not possess satisfactory performance.On the other hand, when the water yield surpasses 3000 parts of weight, the gel-strength of water absorbent polymer reduces greatly, this just is difficult under the situation that keeps polymer morphology and is converted into matrix material, thereby causing the metamorphosis of gained matrix material, this has not only reduced the performance of material but also has made time of drying and drying cost increases.
When water absorbent polymer was drying regime, the added water yield as mentioned above.Used water absorbent polymer also can contain the part or all of above mentioned water yield, that is: according to the present invention in the water absorbent polymer of preparing drying and be directly used in the production of composite material of imbibition not.
If necessary composite material of imbibition can carry out drying after mixing.The exsiccant method is not particularly limited, and can select appropriate means for use, as at room temperature normal pressure or drying under reduced pressure, perhaps static or stir under heat drying.
Based on handling property and the water-retaining capacity of considering product, the dried water content of composite material of imbibition is generally 50%(weight) or it is lower, preferably 30% or still less, 20% or better more at least.
Bulk specific gravity by the prepared composite material of imbibition of the present invention is 0.03～0.7 gram/cubic centimetre, 0.05～0.6 gram/cubic centimetre better.
Water-absorbing polymer (A), water-insoluble inorganic materials (B), water-insoluble hydrophilic fibers material (C) are in following state when forming composite material of imbibition of the present invention, that is to say that water-insoluble water wetted material and water-insoluble inorganic materials are with following state and water absorbent polymer acting in conjunction and constitute matrix material.
Water-insoluble hydrophilic fibers material
1. pars fibrosa or all be embedded in the polymkeric substance.
2. fiber laydown is on polymer surfaces.
3. fiber twines mutually and is embedded in the polymkeric substance or is deposited on the polymer surfaces.
4. polymkeric substance and fiber are that medium is bonded together with the inorganic materials.
The water-insoluble inorganic materials
1. inorganic materials partly or entirely is embedded in the polymkeric substance.
2. inorganic materials is deposited on polymer surfaces.
3. inorganic materials be deposited on as top filamentary material 1.～4. described on the fiber of state.
4. inorganic materials is condensed and is partially embedded in the polymkeric substance or is deposited on the polymer surfaces.
State when water absorbent polymer (A), water-insoluble inorganic materials (B) and water-insoluble hydrophilic fibers material (C) form composite material of imbibition is as described in the above-mentioned example.But the present invention is not limited in above-mentioned example, and (A), (B) and actual keying action (C) are enough in the present invention.
Contain the imbibition ability that water-insoluble inorganic materials and water-insoluble hydrophilic fibers material have improved material greatly in the matrix material of the present invention, particularly to the receptivity of high viscosity liquid.It is believed that its effect is as follows.
After water-absorbing polymer is coated with water-insoluble hydrophilic fibers material, not only improved adaptability to the aqueous solution, and both made direct contact liq of polymkeric substance, as long as its water-insoluble hydrophilic fibers material coating contacts with liquid, just can make polymers swell, be sent in the polymkeric substance because liquid state is a guide functions by fiber.
Used inorganic materials is preferably water insoluble substantially but to a certain degree water absorbability is arranged among the present invention.Inorganic materials partly comprises in the polymkeric substance.Water-absorbing polymer with smooth surface is coated with the fine and close inorganic materials in small, broken bits of last layer, thereby the wicking action that produces the inorganic material particle gap has thus improved the receptivity of water absorbent polymer.Therefore water-insoluble inorganic materials and water-insoluble hydrophilic fibers material the two improved the performance of material with combining of water absorbent polymer, reached purpose of the present invention.
Fig. 1 is the sectional view of various concrete absorbent products among the present invention.Fig. 2 is the skeleton view of movable formula woman's waist model.Fig. 3 is the sketch of rate of adsorption survey meter.
1. hydraulic permeability surfacing.(nonwoven fabric)
2. the impermeable impervious material of liquid.(waterproof layer)
3. paper or nonwoven fabric.
4. composite material of imbibition.
5. paper pulp of Fen Suiing or cellulose powder.
6. fixing strip.
7. crepe paper.
8. artificial cellosilk.
9. movable formula women's waist model.
10. dropper.
11. specimen.
12. minim pipette upper shed.
13. sample anchor.
14. breather hole.
15. glass sand strainer.
Above-mentioned composite material of imbibition self is not satisfied absorbent among the present invention, only has to be used in combination the required effect of competence exertion with flocculence or stratified material.
Particularly, only have when composite material of imbibition embeds in the capillary structure of fibre, it just has space, the Liquid Penetrant ability of the storaging liquid that the fiber combinations material has and keeps the ability of shape.
The material that is used in combination with composite material of imbibition preferably has absorption, infiltration and the reserve capability to liquid. Several special examples are hydrophilic cellulose fibre such as paper pulp, and staple fibre and cotton also have the polyester through hydrophilic treated in addition, and microporous vinylon and acrylic fiber are permitted in the surface.
Because these fibers are highly hydrophilic, they can with liquid rapid permeability fibre inside, can preserve liquid by stronger capillarity simultaneously.
In other words, these fibers can be sent to liquid in the liquid absorption composite and the absorbing state that keeps liquid until this composite reaches capacity by suction-operated and osmosis effectively.
In addition, except above-mentioned hydrophilic fibre cellulose fiber, also can use the synthetic fibers with higher wetting/dry strength ratio, such as polyethylene, polypropylene and polyester fiber, also have the polyethylene-polypropylene composite fibre, they can improve absorbent material even the structural stability in the imbibition process, prevent slip and the consume of absorbent material.
The performance of imbibition material can be improved greatly when above-mentioned two kinds of fibers use on demand jointly obviously.
Make a presentation according to sectional view existing various entities shown in Figure 1 the absorbent article among the present invention.But, it is evident that the present invention is not limited in these entities.
Fig. 1 (a) is sheet imbibition goods of the present invention.This layered article makes with the following method.Equably absorbent composites 4 is placed put again on ply of paper or the nonwoven fabric 3 another layer paper or nonwoven fabric 3 ', spray a spot of water smoke or water vapor thereon, dry then gained stratiform thing is so that the paper or the non-woven fibre 3 of its upper and lower layer, 3 ' be bonded together by the composite material of imbibition 4 of wetting mistake in advance, thus a kind of stratiform absorbent article of snappiness excellence obtained.The consumption of composite material of imbibition preferably 10 grams/square metre～300 grams/square metre, if 30 grams/square metre～150 grams/square metre then better.
Fig. 1 (b) is the entity of another stratiform imbibition goods of the present invention.Its preparation method is: paper pulp or the cellulose powder 5 pulverized are mixed with water-absorbent composite material 4, the gained mixture is molded into stratiform, it is sandwiched in the upper and lower layer of paper or nonwoven fabric 3, with the end seal of tackiness agent, thereby obtained having excellent flexible stratiform absorbent article with upper and lower layer paper or non-woven fibre.
Fig. 1 (c) is the sectional view of a kind of imbibition goods example among the present invention.Its preparation method is: equably composite material of imbibition 4 is placed on the pulp layer 5 that is laminated to the pulverizing on the fixing strip 6 paper pulp of pulverizing 5 is pressed on the matrix material, put fixing strip 6, whole material is covered, and bottom covers with waterproof layer 2, and the upper strata covers with nonwoven fabric 1.Ply of paper or nonwoven fabric 3 can be positioned between the pulp layer 5 of liquid-absorbent matrix material 4 and pulverizing.The material of this structure mainly is suitable for doing paper nappy.
Fig. 1 (d) is the sectional view of another imbibition goods of the present invention.Its preparation method is: composite material of imbibition 4 is placed equably on the paper pulp 5 that is pressed in the pulverizing on the fixing strip 6, lamination is 1～10 layer altogether, best 3～6 layers of crepe paper 7, one side at crepe paper 7 adds waterproof layer 2, one side at the paper pulp of pulverizing is pressed one deck regenerated fiber 8, and whole goods are coated with nonwoven fabric 1.The material of this structure is suitable for doing sanitary towel.
Imbibition goods of the present invention are by water-absorbing polymer (A), water-insoluble inorganic materials (B), the imbibition mixture that water-insoluble hydrophilic fibers material (C) is formed, it demonstrates receptivity and save power to the excellence of high viscosity liquid such as blood, fester, urine.These liquid were to be difficult to absorb and keep with former imbibition goods.The viscosity of this product surface obviously reduces and reduced mainly due to goods fails to absorb and keeps these liquid and the seepage that takes place from the edge.
The present invention is described further according to following example.It is not limited to these examples.Having been derived by it has the imbibition goods of excellent adsorptive power to high viscosity liquid.Because can analyze these imbibition goods with identical notion basically, be that typical imbibition goods are described in detail with sanitary towel here.
The saturated absorption capacity of composite material of imbibition, absorption rate and receptivity, amount and the dynamic adsorption maximum value of returning liquid are measure of effectiveness indexs of the present invention.These will be measured with following method.
Physiological saline will be as typical low-viscosity (mobile) liquid, and blood is as typical high viscosity liquid.
(1) saturated absorption capacity:
The exsiccant composite material of imbibition immersed in the horse blood (taking off fine blood, the product at Nippon biological products center) of q.s or the physiological saline left standstill 30 minutes, filter (filter paper is No. 2, and diameter is 125 millimeters) with suction filter then, weigh.With the above-mentioned system that does not add composite material of imbibition is that reference repeats as above process (promptly only being reference with filter paper), weighs.The saturated absorption capacity of composite material of imbibition can above-mentioned gained data calculate by following formula:
Saturated absorption capacity (gram/gram)=(W
1-W
0)/W
W wherein
1: the weight (gram) of the water absorbent polymer in the composite material of imbibition (A)
W
0: composite material of imbibition after the absorption and the gross weight of filter paper (gram)
W: the weight (gram) of absorption back filter paper
(2～1) absorption rate (a):
Absorption rate is with Instrument measuring shown in Figure 3.Close drop-burette switch 12 suitable for reading, sample anchor 13 and breather hole 14 are fixed on the same horizontal plane.Put 0.3 gram imbibition material 4 on the glass sand strainer (No. 1) 15 of 10 millimeters of the diameters on the sample anchor.Matrix material is placed on the amount of taking off fine horse blood that strainer absorbed in last 20 minute and is absorption rate (a).
(2～2) absorption rate (b):
Repeat absorption rate measuring method (a) in (2～1), determine composite material of imbibition that fixed contains 0.3 gram water absorbent polymer (A) in one minute to the adsorptive capacity of physiological saline, the data that obtain are absorption rate (b).
(3) receptivity:
Take off fine horse blood with 0.5 milliliter or physiological saline drops on the imbibition material with dropper, can observe the situation of absorption, and evaluate by following level Four:
◎: liquid is absorbed immediately.
Liquid is absorbed after zero: 2～3 seconds.
△: liquid is absorbed by adaptation progressively.
*: still have unabsorbed liquid to exist after 1 hour.
(4) the rework solution scale of construction:
Add the false blood of 10 grams in specimen, pressurization 50 gram/square centimeters absorb the liquid that returns with filter paper.The weight that gained returns liquid is defined as the rework solution scale of construction.
(5) maximum dynamically absorbed dose
Movable formula women's waist model 9 shown in Fig. 2 (a) is made up of the specimen 11 shown in Fig. 2 (b) and pants.The walking movement state that this model is in be equivalent to 50 meters/minute injects false blood by dropper 10 simultaneously, the amount of absorbed liquid when just seepage having occurred so as to measuring the edge.
Example 1
Agitator is being housed, and reflux condensing tube adds 230 milliliters of hexanaphthenes and 1.0 gram ethyl cellulose (N-100 in 500 milliliters of four-hole round-bottomed flasks of dropping funnel and nitrogen inlet; Hercules company product), mixture is warming up to 75 ℃.In addition, in an Erlenmeyer flask,, be 45%(weight thereby obtained monomer content with in the 39 gram water and 13.4 aqueous solution that are mixed with of gram caustic sodas and 30 gram vinylformic acid) the aqueous solution (water-content is 55%).Then 50 milligrams of Potassium Persulphates and 65.5 milligrams on average being contained 12 unitary polyoxyethylene glycol diacrylates of oxygen ethylidene adds in the monomer solutions and makes it to be dissolved into homogeneous phase.This monomer solution splashes in the above-mentioned four-hole bottle in 1.5 hours under nitrogen protection and makes it polymerization.Keep 70～75 ℃ of temperature of reaction, post polymerization was complete in 0.5 hour.
With the polymerisate filtering separation and in 80 ℃ of vacuum-dryings, promptly get water absorbent polymer (A-1).
With 20 gram water absorbent polymers (A-1), 100 grams are through the water of ion-exchange, 10 gram bentonite, 10 gram cellulose powder (CFLL, Whatman company product, staple length is 500 microns) place the dual-purpose machine of kneading-mixing to mix about 10 minutes, products therefrom is composite material of imbibition in 80 ℃ of vacuum-dryings.
Under electron microscope, observe composite material of imbibition, find that bentonite and cellulose powder have been fixed on the surface of water absorbent polymer (A-1).The bulk specific gravity of this matrix material is 0.24 gram/cubic centimetre.
Example 2
In being housed, the 500ml four-hole round-bottomed flask of agitator, reflux condensing tube, dropping funnel, nitrogen inlet adds 230ml hexanaphthene and 1.0 gram ethyl cellulose (N-100; Hercules company product), mixture is warming up to 75 ℃.In addition, in Erlenmeyer flask, be dissolved in the aqueous solution that 39 grams are mixed with in the water and 30 gram vinylformic acid, obtain containing monomer 45%(weight with this with 13.4 gram caustic sodas) the aqueous solution (water-content is 55%).Add 50 milligrams of Potassium Persulphates in the monomer solutions and make it to be dissolved into homogeneous phase.This monomer solution was added dropwise under the nitrogen protection in the above-mentioned four-hole round-bottomed flask in 1.5 hours makes it polymerization.Holding temperature is at 70～75 ℃, and post polymerization was complete in 0.5 hour.
With gained polymerisate azeotropic dehydration (under the hexanaphthene reflux conditions), the water content that is distributed to the polymkeric substance in the hexanaphthene with adjusting is in 35%(weight).
Be dissolved with the 1 ml water solution that 0.03 gram three contracts four glyceryl alcohols, four glycidyl ethers (trade(brand)name: Denacol Ex-512, Nagase company product) 73 ℃ of addings then, the gained mixture kept 2 hours under this temperature, removed hexanaphthene.Resulting polymers promptly gets water absorbent polymer (A-2) 80 ℃ of following vacuum-dryings.
With 20 gram water absorbent polymers (A-2), 200 grams are through the water of ion-exchange, 10 gram bentonite, 10 gram cellulose powders repeat the process in the example 1, obtain containing water absorbent polymer (A-2) and be fixed on bentonite on the polymkeric substance and the composite material of imbibition of cellulose powder, its bulk specific gravity is 0.27 gram/cubic centimetre.
Example 3
Repeat the step in the example 1, but in order to change the composition of composite material of imbibition, replace bentonite with 10 gram aluminum oxide, amount through the water of ion-exchange is 60 grams, so just obtained containing water absorbent polymer (A-1) and be fixed in aluminum oxide on the polymkeric substance and the composite material of imbibition of cellulose powder, its bulk specific gravity is 0.21 gram/cubic centimetre.
Example 4
Repeat the step of example 1, yet in order to change the composition of composite material of imbibition, replace cellulose powder with 20 gram paper pulp (5 millimeters of staple lengths), the amount of water absorbent polymer (A-1) is 10 grams, get final product to such an extent that contain water absorbent polymer (A-1) and be fixed in bentonite on the water absorbent polymer and the composite material of imbibition of paper pulp, its bulk specific gravity is 0.26 gram/cubic centimetre.
Example 5
White powdered water-insoluble water absorbent polymer (A-3) discloses example 4 described method preparations in 62463/1986 by W-Gum, vinylformic acid, acrylamide and Ethylene glycol dimethacrylate according to Japanese Patent.
Repeat the step of example 1 with the as above water absorbent polymer of gained (A-3), obtained containing water absorbent polymer (A-3) and be fixed in bentonite on the water absorbent polymer and the composite material of imbibition of cellulose powder, its bulk specific gravity is 0.22 gram/cubic centimetre.
Example 6
2 gram bentonite and 100 are restrained water after spiral rotary blade stirrer for mixing, add employed water absorbent polymer (A-1) and 2 gram cellulose powders in the 20 gram examples 1 continuously, mediated then 5 minutes, products therefrom promptly gets 80 ℃ of following vacuum-dryings and contains water absorbent polymer (A-1) and be fixed in bentonite on the water absorbent polymer and the composite material of imbibition of cellulose powder, and its bulk specific gravity is 0.52 gram/cubic centimetre.
Example 7
Repeat the step of example 1, but in order to change the composition of composite material of imbibition, the bentonite that adds and the amount of cellulose powder respectively are 200 grams, thereby obtained containing water absorbent polymer (A-1) and be fixed in bentonite on this polymkeric substance and the composite material of imbibition of cellulose powder, its bulk specific gravity is 0.08 gram/cubic centimetre.
Case of comparative examples 1
Water absorbent polymer (A-1) prepared in the example 1 is used as case of comparative examples 1.
Case of comparative examples 2
Repeat the step of example 1, but do not add cellulose powder, promptly obtained containing water absorbent polymer (A-1) and the composite material of imbibition of the bentonite that is fixed thereon, its bulk specific gravity is 0.81 gram/cubic centimetre.
Case of comparative examples 3
Repeat the step of example 1, but do not add bentonite, promptly obtained containing the water absorbent polymer (A-1) and the fixing composite material of imbibition of the cellulose powder on the water absorbent polymer, its bulk specific gravity is 0.31 gram/cubic centimetre.
For by example 1～7, saturated absorption capacity, absorption rate, the receptivity of each composite material of imbibition that case of comparative examples 1～3 is prepared are evaluated.The results are shown in table 1 and the table 2.
Table 1
Assessment
Saturated absorption amount absorption rate (a) receptivity
(gram/gram) (milliliter/0.3 gram)
Horse blood horse blood horse blood
Example 1 31.2 2.8 ◎
Example 2 24 2.3 ◎
Example 3 30.1 3.1 ◎
Example 4 19 2.9 ◎
Example 5 22 2.5 ◎
Example 6 18 2.2 zero
Example 7-2.4 0～◎
Case of comparative examples 16 1.2 △
Case of comparative examples 2 12 1.9 △
Case of comparative examples 3 15 1.6 ◎
Table 2
Assessment
Saturated absorption amount absorption rate (b) receptivity
(gram/gram) (milliliter/0.3 gram)
Physiological saline physiological saline physiological saline
Example 1 60 6.8 ◎
Example 2 54 7.4 ◎
Example 3 56 6.0 ◎
Example 4 50 6.8 ◎
Example 5 52 6.3 ◎
Example 6 57 5.8 ◎
Case of comparative examples 1 58 3.4 zero
Case of comparative examples 2 57 4.1 zero
From table 1 and table 2 as can be seen, composite material of imbibition of the present invention still is that the material all compared in the example according to the facts of high viscosity liquid has better receptivity to low-viscosity (mobile) liquid.Particularly they have saturated absorption capacity, absorption rate and the receptivity to high-viscous liquid of unprecedented excellence.
Example 8
The polymkeric substance (A-2) of gained in the 20 gram examples 2,200 grams under agitation mixed 5 minutes in the dual-purpose machine of adding kneading-mixing continuously through the water and the 5 gram kaolin of ion-exchange, added 5 gram kaolin and 10 gram cellulose powders then.The gained mixture is mediated after 15 minutes 80 ℃ of vacuum-dryings, promptly get one and contain the kaolin on water absorbent polymer (A-2) and the fixed polymer and the composite material of imbibition of cellulose powder, its bulk specific gravity is 0.22 gram/cubic centimetre, and water-content is a 8%(weight).
Example 9
Repeat the step of example 1, but replace bentonite with 10 gram aluminum oxide, with 20 water that restrain through ion-exchange, and need not 100 gramion water, not with liquid form, but add with spray method.Obtain containing water-absorbing polymer thus and be fixed in aluminum oxide on the water absorbent polymer and the composite material of imbibition of cellulose powder.Its bulk specific gravity is 0.22 gram/cubic centimetre, water-content 8%(weight).
Example 10
10 gram water absorbent polymers (A-1) are added in the 500 gram hexanaphthenes, stir and drip 100 gramion exchanged waters down, add 10 gram kaolin and 10 gram paper pulp (5 millimeters of staple lengths) then, stirred 1 hour, the products therefrom filtering separation is also dry, promptly get and contain water absorbent polymer (A-1) and be fixed in kaolin on the polymkeric substance and the composite material of imbibition of paper pulp, its bulk specific gravity is 0.16 gram/cubic centimetre, and water-content is a 13%(weight).
Example 11
Polymkeric substance (A-3), 200 grams of 10 grams by example 5 gained are added in the bitubular blending machine of rotary container type continuously through water, 100 gram talcum powder and the 100 gram cellulose powders of ion-exchange, and blending machine rotated about 1 hour.The gained mixture is 80 ℃ of following vacuum-dryings.Promptly get and contain water absorbent polymer (A-3) and be fixed in talcum powder on the polymkeric substance and the composite material of imbibition of cellulose powder, its bulk specific gravity is 0.25 gram/cubic centimetre, water content 16%(weight).
Example 12
Repeat the step in the example 1, but will mediate-mix dual-purpose machine and be heated to 80 ℃ and kneading process is carried out in airtight kneading-mixing machine, promptly get and contain water absorbent polymer (A-1) and be fixed in bentonite on the polymkeric substance and the composite material of imbibition of cellulose powder, its bulk specific gravity is 0.22 gram/cubic centimetre, and water content is a 9%(weight).
Case of comparative examples 4
The method that water absorbent polymer (A-1), bentonite and cellulose powder are pressed in the example 1 is mixed, but do not add water through ion-exchange.Observation post gets mixture and finds that bentonite and cellulose powder are not fixed on the water absorbent polymer (A-1) under electron microscope, and the packing ratio of this mixture must be 0.25 gram/cubic centimetre.
Case of comparative examples 5
Repeat the operation of example 1, but add is 800 grams through the amount of the water of ion-exchange.In the pasty state, this not only makes mediates difficult treatment but also needs the long time carry out thereafter dry and pulverize when mixture is being mediated.The bulk specific gravity of the matrix material of gained is 0.31 gram/cubic centimetre, and water-content is a 18%(weight), observation shows that most of bentonite and cellulose powder are contained in the matrix material under the Electronic Speculum.
For measuring, the results are shown in Table 3 and table 4 by saturated absorption capacity, absorption rate and the receptivity of gained composite material of imbibition in example 8～12 and the case of comparative examples 4～5.
Table 3
Assessment
Saturated absorption amount absorption rate (a) receptivity
(gram/gram) (milliliter/0.3 gram)
Horse blood horse blood horse blood
Example 8 28.5 3.5 ◎
Example 9 27.4 3.0 ◎
Example 10 29.2 2.5 0
Example 11 26.3 3.4 0～◎
Example 12 27.1 3.4 ◎
Case of comparative examples 4 11.8 1.5 zero
Case of comparative examples 5 14.2 1.8 △
Table 4
Assessment
Saturated absorption amount absorption rate (b) receptivity
(gram/gram) (milliliter/0.3 gram)
Physiological saline physiological saline physiological saline
Example 8 58 7.9 ◎
Example 9 59 7.5 ◎
Example 10 57 6.6 ◎
Example 11 53 7.7 ◎
Example 12 56 7.8 ◎
Case of comparative examples 4 57 4.1 zero～◎
Case of comparative examples 5 59 5.0 zero～◎
From table 3 and table 4 data as can be seen, the matrix material of producing with novel method of the present invention all is excellent to the receptivity of high-viscous liquid still to the thin fluid body.Particularly outstanding is with regard to high viscosity, and its saturated absorption capacity, absorption rate and receptivity all obviously are better than the material in the case of comparative examples.
Example 13
With 20 gram water absorbent polymer (A)-sodium polyacrylates, 100 grams are through the water of ion-exchange, 10 gram water-insoluble inorganic materials (B)-bentonite and 10 gram water-insoluble hydrophilic fibers material (C)-cellulose powder (CFLL, Whatman company product, staple length is about 500 microns), put into dual-purpose kneader and mediated 10 minutes, products therefrom gets composite material of imbibition 80 ℃ of following vacuum-dryings.Electron microscopic observation shows that bentonite and cellulose powder all are fixed on the surface of water absorbent polymer.The bulk specific gravity of this matrix material is 0.24 gram/cubic centimetre.
Prepare composite material of imbibition by above-mentioned same method, but by the such water absorbent polymer (A) that changes shown in the table 5, water-insoluble inorganic materials (B), water-insoluble hydrophilic fibers material (C).
The receptivity of the composite material of imbibition that so obtains is listed in table 5.In order to compare, only contain the control sample of water absorbent polymer (A), only contain the control sample of water absorbent polymer (A) and water-insoluble inorganic materials (B) and only contain water absorbent polymer (A) and the receptivity of the control sample of water-insoluble hydrophilic fibers material (C) is also listed in table 5.
Have composite material of imbibition and control sample material preparation that the sanitary napkin of structure shown in Fig. 1 (d) obtains with aforesaid method.
In preparation during sanitary napkin, water accepting layer formed by 0.6 gram composite material of imbibition, 2.0 gram fluffed pulps, 1.5 gram thieving papers, 0.3 gram regenerated fiber and upper layer be use by 65% trevira and 35% polyethylene/polypropylene conjugated fibre forms have area density be 20 restrain/square metre the Thermoadhesive nonwoven fabric prepare.In addition, the lamination of being made up of the polyethylene of waterproof paper (25 gram/square metre) and 10 micron thickness is as waterproof layer.
The liquid amount of returning of the sanitary napkin that so obtains and the maximum measurement result that dynamically absorbs are shown in table 5.
Absorbent article of the present invention as can be seen from Table 5 has excellent receptivity to high-viscous liquid such as blood.
Claims (7)
1, by water absorbent polymer (a), water-insoluble inorganic materials (b), water-insoluble hydrophilic fibers material (c) is pressed (a), (b), weight ratio 100:5 (c)～1200:5～1200 composite material of imbibition of being formed.
2, the matrix material described in the claim 1, its bulk specific gravity are 0.03～0.7 gram/cubic centimetre.
3, the matrix material described in the claim 1, wherein polymkeric substance (a) is polymkeric substance or its cross-linking products of water-soluble ethylenically unsaturated monomers, major ingredient has vinylformic acid or acrylate.
4, the described matrix material of claim 1, wherein inorganic materials (b) is selected from aluminum oxide, silicon, zeolite, polynite family clay, kaolin group's clay.
5, matrix material described in the claim 1, wherein filamentary material (c) is natural or the Mierocrystalline cellulose of synthetic.
6, the method for preparing defined water-absorbent composite material in the claim 1 comprises with 100 parts of weight (a) being that benchmark mixes (a) in the presence of the water of 70～3000 parts of weight, (b), and (c).
7, the method described in the claim 6 also comprises the drying step of mixture.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62017946A JPH0720548B2 (en) | 1987-01-28 | 1987-01-28 | Liquid-absorbent complex |
| JP17946/87 | 1987-01-28 | ||
| JP80089/87 | 1987-04-01 | ||
| JP101468/87 | 1987-04-24 | ||
| JP62101468A JPH0720549B2 (en) | 1987-04-24 | 1987-04-24 | Method for manufacturing absorbent composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN88100333A true CN88100333A (en) | 1988-08-24 |
| CN1012617B CN1012617B (en) | 1991-05-15 |
Family
ID=26354540
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88100333 Expired CN1012617B (en) | 1987-01-28 | 1988-01-28 | Absorbent composite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1012617B (en) |
-
1988
- 1988-01-28 CN CN 88100333 patent/CN1012617B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN1012617B (en) | 1991-05-15 |
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