CN108192014A - Super absorbent resin containing acid deodoriging properties - Google Patents
Super absorbent resin containing acid deodoriging properties Download PDFInfo
- Publication number
- CN108192014A CN108192014A CN201711416581.7A CN201711416581A CN108192014A CN 108192014 A CN108192014 A CN 108192014A CN 201711416581 A CN201711416581 A CN 201711416581A CN 108192014 A CN108192014 A CN 108192014A
- Authority
- CN
- China
- Prior art keywords
- acid
- water
- absorbent resin
- super absorbent
- methyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 229920005989 resin Polymers 0.000 title claims abstract description 92
- 239000002250 absorbent Substances 0.000 title claims abstract description 57
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- 239000002253 acid Substances 0.000 title claims abstract description 34
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000004332 deodorization Methods 0.000 claims abstract description 14
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- 150000003839 salts Chemical class 0.000 claims description 15
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 10
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 5
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- 239000011259 mixed solution Substances 0.000 claims 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims 1
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- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 6
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- 239000002738 chelating agent Substances 0.000 description 6
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- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 4
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/46—Deodorants or malodour counteractants, e.g. to inhibit the formation of ammonia or bacteria
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
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Abstract
The present invention relates to a kind of super absorbent resin containing acid deodoriging properties, including：(a) deodorant：In acidity, in specific acid condition (pH<6.7) property is stablized under; it is more sensitive to the pH responses of environment; it is solid granulates or powder; can also be the solution of solvent; either pure liquid; the deodorant volatile performance is weak, and the remaining time in super absorbent resin is long, and the additive amount based on super absorbent resin is 0.05 1wt%；(b) unsaturated acrylic monomer, (c) crosslinking agent.After super absorbent resin surface treatment, deodorization component is added thereto, makes other performances of the resin will not be by too big influence, but there is apparent fast deodorization performance.
Description
Technical field
The present invention relates to a super absorbent resin containing acid deodoriging properties, deodorizing effect significantly increases, composition and its
Manufacturing method.More particularly to suitable for absorbent commodity, such as：Adult diapers' (disposable diaper), sanitary napkin, incontinence pad,
In the products such as mattress, pet pads, Wound care material, construction material, wastewater treatment, and the polypropylene with smelly eliminating absorbent
The manufacturing method of sour water-absorbent resin, composition and other absorbent articles.
Background technology
High water absorbency polymer (Super absorbent polymer, SAP) is also known as high hydroscopic resin, is that one kind contains
Strongly hydrophilic group, it is not soluble in water, but the cross-linked polymer of tens of, hundreds of or even thousands of times of water of dead weight can be absorbed.High water absorption
Resin is now widely used in a variety of necks of the amenities and soil moisturizing agent etc. such as paper diaper, physiological hygiene cotton, adult-incontinence articles
Domain.
Absorbent article disposable diaper, sanitary napkin, Pantiliner, incontinence pad, tampon etc. are commonly used in absorber
Liquid, such as urine, excrement, vaginal fluid and through liquid.After these fluids are absorbed, it is found that absorbent article includes many volatilizations
Property compound, the compound includes with the aliphatic acid (such as isovaleric acid) of unpleasant smell, sulfur-containing compound (such as sulphur
Alcohol and sulfide), ammonia, amine (such as triethylamine), ketone (such as 4- heptanone), alcohol and alcohol (class alcohol), the smell is in the phase of wearing
Between or while handling released from these products.The compound may be present in body fluid or be absorbed into absorption in fluid
It is generated at any time via chemical reaction and/or fluid degradation mechanism when in product.In addition, oneself is absorbed into absorption system in body fluid
After in product, they usually equally can generate the microorganism of stench by-product and/or enzyme contacts, the degradation with due to degradation mechanism
Such as corrupt degradation of mechanism, acid degradation, protein degradation, fat acid decomposition.These smells can lead to the dress of absorbent article
Person and processor equally meet with unpleasant impression, and the concealed use of absorbent article and/or processing can be made to become difficult.
And the body fluid of human body, urine is refered in particular to herein, and generally in faintly acid, and acrylic acid series super absorbent resin is using
In the process, faintly acid is also presented, so that the use of many deodorant is restricted, such as sodium bicarbonate.May not have
It has just been reacted before contacting body fluid with the acidic materials in system, and then deodorizing effect declines.
The technology of existing deodorization mainly includes three kinds：(1) by physical absorption adsorb malodor molecules (such as
EP0295438B、WO1994022502A、EP0644207B、EP0538983B、US20050137546A、CN102225981A、
US20120258851A、CN103857714A、CN1668343A、CN1296981A、CN101050244A、CN101143913A、
CN101423588A、CN104448155A、CN102311557A、CN104448102A、CN103214616A、
CN103476811A、CN103857714A、CN105377921A、CN102317329A、CN102010560A)；(2) macromolecular packet
Wrap up in malodor molecules (such as EP0591168A)；(3) it chemically reacts, mainly there is acid-base neutralization, also other inorganic polymer composite flocculants
(such as WO2001089591A)；Wait strategies.
In deodorization technology, it is known that have using zeolite, bentonite other inorganic powders, gel, silica gel, aldehydes, quinones,
Or addition aromatic.
But these current methods, all it is that deodorization ingredient is mixed in high water absorption system resin or the product is coated in height
The surface of water-absorbing resins, but the state that super absorbent resin quickly absorbs water in itself so that the non-complete body fluid of deodorization is inhaled
It receives inside high hydroscopic resin, can not be contacted with deodorization ingredient, so that deodorizing effect declines or is to use one merely
Kind of substance uses a system, can not solve the initial stink of body fluid because body fluid have at the very start it is initial smelly
Taste or using covering, physical absorption etc. again cannot remove stink from root, such as when absorbent is acted on by external force,
Internal body fluid flow goes out, and stink again can be with the efficiency low consumption duration of its generation either reaction, it is impossible to stink is quickly removed, thorough
Before removing stink, stink artistic conception allows people to feel under the weather.Aromatic is commonly used in absorbent article enhancing user to production
The impression (such as release of pure and fresh fragrance) of product, these aromatic are usually added in low content, and in product entirely using following
Faint odor control benefit is only provided in ring.In addition, general physical absorption system, such as activated carbon, usually not with fragrance
Agent is compatible so that deodouring effect is had a greatly reduced quality.
Invention content
Present invention aims at provide a kind of super absorbent resin of acid deodoriging properties, it is especially useful in adult diaper,
For escaping gas, such as ammonia, amine, thio-alcohol stink has the deodorising product of positive effect.
In order to solve described problem, the present invention adds deodorization component thereto after super absorbent resin surface treatment,
Make other performances of the resin will not be by too big influence, but there is apparent fast deodorization performance.The product is suitable for adult's paper
Urine pants, pet urine pad, women physiological period nursing health product and other needs quickly go to the place to eliminate the unusual smell.
The present invention provides a kind of super absorbent resin of acid deodoriging properties, a kind of high-hydroscopicity containing acid deodoriging properties
Resin, including：(a) deodorant：In acidity, in specific acid condition (pH<6.7) property is stablized under, and the pH of environment is rung
Should be more sensitive, it is the solution of solid granulates or powder or solvent or pure liquid, the deodorant
Volatile performance is weak, and the remaining time in super absorbent resin is long, and the additive amount based on super absorbent resin is 0.05-1wt%；
(b) unsaturated acrylic monomer, (c) crosslinking agent.
The invention discloses a kind of super absorbent resin containing acid deodoriging properties, excellent effect can quickly go deodorization
Taste, and do not generate the substance of other pollution environment, and buildup of resin density will not be reduced excessively, and do not influence resin conduction and
It is distributed the imbibitions characteristics such as the absorptive capacity under the ability of liquid, liquid-keeping property, pressure.
Specific embodiment
The super absorbent resin containing acid deodoriging properties of the present invention is described in detail, but the scope of the present invention below
It is not limited to these explanations.
A kind of super absorbent resin of acidity deodoriging properties, a kind of super absorbent resin containing acid deodoriging properties, packet
It includes：(a) deodorant：In acidity, in specific acid condition (pH<6.7) property is stablized under, more quick to the pH responses of environment
Sense, is the solution of solid granulates or powder or solvent or pure liquid, the deodorant volatile performance
Weak, the remaining time in super absorbent resin is long, and the additive amount based on super absorbent resin is 0.05-1wt%；(b) insatiable hunger
And acrylic monomer, (c) crosslinking agent.
1.1 monomer solution
Obtain the step of containing unsaturated acrylic monomer and cross-linking agent aqueous solution.It is specifically described below.
Monomer (monomer) used in the present invention can be formed by free radical polymerization and be inhaled to contain unsaturated double-bond
Monomer of the Mono-olefinic unsaturation containing acid groups of water-base resin, is not particularly limited.It can be listed below：Acrylic acid, methyl
Acrylic acid, ethylacrylic acid, α-chloroacrylic acid, alpha-cyanoacrylate, Beta-methyl acrylic acid (crotonic acid), atropic acid,
β-acryloxy propionic, sorbic acid, α-chlorine sorbic acid, 2 '-methyl iso-crotonic acid, cinnamic acid, p- chloro-cinnamic acid, β-tristearin
Acid, itaconic acid, citraconic acid, mesaconic acid, glutaconate, aconic acid, maleic acid, cinnamic acid, fumaric acid, tricarboxylic ethylene and maleic acid
Acid anhydride, particularly preferred acrylic acid and methacrylic acid, most preferably acrylic acid.
It can be copolymerized using other class monomers with the monomer containing carboxyl.It can be listed below：Vinyl sulfonic acid, alkene
Propyltoluene sulfonic acid, vinyl toluene sulfonic acid, styrene sulfonic acid, 2- (methyl) acrylamide-2-methyl propane sulfonic, 2- (methyl)
The anionic properties such as acryloyl group ethanesulfonic acid, 2- (methyl) acryloyl groups propane sulfonic acid, (methyl) acryloyl group phosphoric acid 2- hydroxy methacrylates
Unsaturated monomer and its salt；Unsaturated monomer containing sulfydryl；The unsaturated monomer of phenolic hydroxy group；(methyl) acrylamide, N- second
The unsaturated monomer of the amide-containings such as base (methyl) acrylamide, N, N- dimethyl (methyl) acrylamide；(methyl) acrylic acid
N, N- dimethyl amido ethyl ester, (methyl) acrylic acid N, N- dimethyl amido propyl ester, N, N- Dimethylaminopropyls (methyl) third
Amino-containing unsaturated monomer such as acrylamide etc..
These unsaturated monomers can be used alone, and can also be mixed with two or more, comprehensive absorbent resin powder
It is preferable to use contain acrylic acid and/or its salt (such as sodium salt, lithium salts, sylvite, ammonium salt, amine etc. for performance and cost
Salt), wherein in terms of cost, the polyacrylic acid water-absorbent resin of the acrylic monomer of more preferable sodium salt.
There is no particular restriction for the neutralization ratio of these undersaturated monomers containing acid groups, can be in part and/or complete
It neutralizes, preferably part neutralizes, and can also optionally neutralize polymeric gel after polymerisation.The unsaturation contains acid groups
The preferred degree of neutralization of monomer is 25~100mol%, particularly preferably reaches at least 40~95mol%, more preferably up to 50~
90mol%.The neutralization of monomer of the unsaturation containing acid groups can carry out before or after the polymerization.Alkali metal hydrogen can be used
Oxide, alkaline earth metal hydroxide, ammonia and carbonate and bicarbonate are neutralized.It is in addition it is possible to use any other
Can with it is described acid formed water soluble salt alkali.It can also be neutralized using a variety of alkali.It is preferable to use ammonia or alkali metal hydrogen-oxygens
Compound neutralizes, and is particularly preferably neutralized using sodium hydroxide.
As polyacrylic absorbent resin powder, the usage amount of acrylic acid and/or its salt relative to whole monomers into
Divide (except crosslinking agent), usually more than 60mol%, preferably more than 75mol%, preferably more than 90mol%, it is further excellent
It is selected as more than 95mol%.
Monomer concentration is also not particularly limited, and the unsaturated monomer containing acid groups and cross-linking agent aqueous solution a concentration of 25~
60wt%, preferably 30~55wt%, further preferred 35~50wt%.In the case of monomer concentration is less than 25wt%, energy is produced
Power can reduce, therefore not good enough.When monomer concentration is higher than in the case of 60wt%, crushing load increases, and production stability is caused to be deteriorated.
The solvent of monomer is water, can also and with a small amount of organic solvent.
As internal crosslinker, the compound for containing multiple vinyl selected from intramolecular, intramolecular contain at least one ethylene
Based compound and it is at least one can have with the compound for the functional group that carboxyl reacts on the unsaturated monomer, intramolecular it is multiple
Can with it is one or more in the compound for the functional group that carboxyl reacts on the unsaturated monomer.Previously many institute's weeks can be used
The internal crosslinking agent known.Specifically, it can for example enumerate：N, N '-methylene-bisacrylamide, trimethylolpropane tris (first
Base) acrylate, ethylene glycol two (methyl) acrylate, polyethyleneglycol diacrylate, polyethylene glycol two (methyl) acrylic acid
Ester, polyethylene glycol diallyl ether, pentaerythritol tetraacrylate, triarylamine, ethylene glycol diglycidylether, ethylene glycol,
1,2- propylene glycol, 1,3- propylene glycol, 1,4- butanediols, glycerine, pentaerythrite, polyethylene glycol and one kind in ethylene carbonate or
It is a variety of, these internal crosslinking agents, it is contemplated that reactivity can use one or more.Wherein, preferred trimethylolpropane tris
In (methyl) acrylate, polyethyleneglycol diacrylate, ethylene glycol diglycidylether, polyethylene glycol, 1,4- butanediols
It is one or more, further preferred trimethylolpropane tris (methyl) acrylate, polyethyleneglycol diacrylate, ethylene glycol two
It is one or more in glycidol ether.
The usage amount of internal crosslinker is determined according to the physical property of required water-absorbing resins, relative to content of monomer, preferably
0.001~5mol%, more preferably 0.005~2mol%, further preferably 0.01~1mol%.If the use of internal crosslinker
Amount is less than 0.001mol%, and the water soluble apparent extract of gained water-absorbing resins increases, and can not substantially ensure the suction under pressurization
Water.If the usage amount of internal crosslinking agent is more than 5mol%, chemical crosslinking density is too high, the absorbent resin powder of gained
Water absorption it is insufficient.In addition, internal crosslinking agent can be once added in reaction system, can also be added batch-wise to reaction system
In.
1.2 polymerization procedure
Polymerization procedure is the step of monomer solution is polymerize.Polymerization process can normal pressure, decompression or pressurization under into
Row, preferably carries out under normal pressure.
As the polymerization initiator used in this step, there is no particular restriction, can use and under polymerization conditions can
It forms free radical and is commonly used for preparing any initiator of water-absorbing resins.It can also be by acting on and can gather electron beam
The water-containing monomer solution of conjunction and cause polymerization.It can also be acted on by high-energy radiation in the presence of photoinitiators poly- to cause
It closes.According to monomeric species, polymerizing condition being polymerize etc., from the polymerization initiator utilized when usually manufacturing water-absorbing resins
Select one or more uses.
Polymerization initiator is preferably peroxide, hydroperoxides, hydrogen peroxide, persulfate and azo-compound.It is excellent
Choosing uses water soluble starter.Specifically enumerate：Heat decomposition type initiator, such as sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate over cure
Hydrochlorate；The peroxide such as hydrogen peroxide, tert-butyl peroxide, methyl ethyl ketone peroxide, azonitrile compound, azo amidification are closed
Object, cyclic annular azo amidine compound, azo amide compound, alkyl azo-compound, bis- (2- amidine propanes) disalts of 2,2 '-azo
The azo-compounds such as bis- [2- (2- imidazoline -2- bases) propane] dihydrochlorides of hydrochlorate, 2,2 '-azo；Or photolysis type initiator,
Such as Benzoin derivative, benzil derivatives, acetophenone derivs, benzophenone derivates, azo-compound.These cause
In agent, with regard to cost and for reducing the ability of residual monomer, preferably heat decomposition type initiator, further preferably persulfuric acid
Salt.
In addition, the decomposition of these polymerization initiators can be promoted by and with reducing agent.Therefore, it is possible to use redox
System initiator.It as the reducing agent, is not particularly limited, can be selected from：Sodium pyrosulfite, sodium sulfite, bisulfite
The sulfurous acid such as sodium (hydrogen) (salt), L-AA (salt), metal salt (such as iron (II) ion or silver ion), amine etc..In oxygen
In the case that change reduction series initiators use oxidative polymerization initiator and reducing agent in this way, it can be closed respectively with monomer solution
Reducing agent, can also be mixed in monomer solution by stream in advance.
When carrying out the polymerization, poly- second two can also be added in the reaction system before polymerization or in polymerization as needed
Alcohol, starch, starch derivatives, cellulose, cellulose derivative, polyvinyl alcohol, polyacrylic acid (salt), polyacrylic acid (salt) crosslinking
The hydrophilic polymers such as body；Or chain-transferring agents, the chelating agent such as ortho phosphorous acid (salt) etc..It, can be preferable as hydrophilic macromolecule
Ground uses water-soluble resin or water-absorbing resins, can improve the viscosity of reaction system.Relative to monomer, hydrophilic polymer
Usage amount is preferably 0~30wt%, more preferably 0.001~20wt%, further preferably 0.01~10wt%.
As the polymerization employed in this step, it is not particularly limited.Free radical polymerization in preferably homogeneous
(such as free radical polymerization in aqueous solution), the precipitation polymerization from organic solvent, suspension polymerisation, emulsion polymerization or mini-emulsion polymerization
Deng.It is preferred that the free radical polyalcohol in homogeneous system, the free radical polymerization in further preferred aqueous solution.Water solution polymerization process has
Make the standing polymerization that monomer solution is polymerize under static condition and the stirring polymerization being polymerize in agitating device
Method etc..In addition, polymerization is divided into batch method according to continuous production and continuity method polymerize.It is particularly suitable for the polymerization solved the problems, such as
It is aqueous solution polymerization, especially continuous conveyor polymerization or continuous kneader polymerization.
The manufacturing device of water-absorbing resins as the present invention, is not particularly limited, preferably continuous conveyor polymerization dress
Put or continuously stir polyplant.
Continuous conveyor polyplant is preferably that the continuous of cyclic annular conveyer belt type stands polyplant, and conveyer belt is fluororesin
System or the conveyer belt to be formed with fluororesin-coated surface.Furthermore it is preferred that have heating unit or attemperator, and have
The device of system that the steam of water generated when polymerizeing and/or monomer solution is recycled and recycled.
It continuously stirs polyplant and uniaxial agitating device may be used, can also use continuous kneader etc. that there is multiple stir
The agitating device of axis is mixed, it is preferable to use multi-shaft stirring device for productive viewpoint.
When polymerization start temperature refers to that initiator adds to monomer solution, the real time temperature of polymerization system.
Pulverising step
The step of aqueous gel shape cross-linked polymer of above-mentioned gained is crushed, pulverising step can polymerization when or
It is carried out after polymerization.Crushing process during polymerization can use kneader, and the crushing after polymerization can use cutting machine, meat grinder
Deng.Preferably 0.5~10 millimeter of gel particle size after crushing, if gel particle is too small, wind that level of residual monomers can be brought higher
Danger if water-setting gum polymers are not crushed or gel particle is too big, cannot obtain final granular product, especially
In subsequent heat drying steps, it is difficult to evaporate the moisture in hydrogel.
1.3 heat-drying step
Heat-drying step is that the aqueous gel shape cross-linked polymer is subject to drying, forms porous structure drying polymerization
Object.Drying is usually in 60~300 DEG C as heating medium temperature, preferably 100~250 DEG C, more preferable 120~220 DEG C of temperature
Degree is lower to carry out.Drying time depends on surface area and the water content of polymer and drier type, is selected to obtain target
Water content (water content passes through in 105 DEG C of dry 3 hours weightless measurements).
Water content for water-absorbing resin of the present invention is not particularly limited, the more preferable 0.2~30wt% of water content, further
It is preferred that 0.3~15wt%, particularly preferred 0.5~10wt%.Too high-moisture not only damages mobility, and therefore influences production,
And make being crushed into for water-absorbing resin can not possibly and may be out of hand to specific size distribution.
It is not particularly limited as used drying means, a variety of methods can be used to obtain target water content, specifically
It enumerates：Heat drying, hot-air are dry, be dried under reduced pressure, infrared drying, microwave drying, by with hydrophobic organic solvent
Azeotropic mixture is dehydrated and using the drying of high-temperature steam high humility.
In addition, foaming agent can pass through further thermal decomposition under the drying temperature, further foaming process is realized.
1.4 grain refineds and screening step
In order to obtain the water-absorbing resins (adjusting grain size jointly with following micro mist granulation process) with specified particle size, need
The step of grain refined is carried out to porous structure cross-linked polymer after drying and is sieved.
For obtaining having irregular pulverized shape, and the absorbent resin that grain size can be controlled effectively, grain refined uses
Machine include shearing crude pulverizer, impact powder pulverizer and high-speed rotation type powder pulverizer.It is and right after grain refined
Resin particle is further sieved.
The Mass median diameter (D50) of water-absorbing resins, is preferably regulated as 200~650 microns, is more preferably adjusted to 200
~550 microns, further preferably it is adjusted to 300~500 microns.Particle fraction control of the diameter less than 150 microns for 0~
8wt%, preferably 0~5wt%, more preferable 0~2wt%.In addition, the fewer diameter the better higher than 850 microns of particle fraction, control
For 0~8wt%, preferably 0~5wt%, more preferable 0~2wt%.In the present invention, it is preferred in 150~850 microns of particle
Ratio carries out surface-crosslinked under conditions of being more than 95wt%, more preferably more than 98wt%.The logarithmic scale of size distribution is inclined
Poor (σ ζ) is preferably controlled to 0.20~0.40, more preferable 0.20~0.38, further preferred 0.20~0.36.
The recycling of 1.5 fine grained water-absorbing resins
In the present invention, small particle fine grained is controlled (less than 150 by the way that fine grained water-absorbing resins are recycled
The particle of micron) yield.
The small particle water absorbing resin particle (particle for being less than 106 microns) obtained by grain refined and screening can pass through return
Polymerize again to monomer solution or mixed with a large amount of hot water carry out agglomeration (weight ratio of little particle water-absorbing resin and hot water be 2:
1~1:2), to revert to water-setting gum-like product again.Then by be granulated, dry and grain refined and etc. readjust as mesh
Mark grain size water absorbing resin particle.Amount of waste can be reduced by the particle for recycling and regenerating beyond target zone.
1.6 surface cross-linking step
In the manufacturing method of the present invention, it further includes using surface crosslinking agent to the water-absorbing resins surface after Sieving and casing
Nearby carry out the step of surface treatment forms covalent bond.By carrying out surface-crosslinked step to the water-absorbing resins after Sieving and casing
Suddenly, the water absorbent rate and permeability for liquids under resin pressurization can effectively be promoted.But for the present invention water-absorbing resin from
Heart water holding capacity (CRC), compared to having and reducing to a certain degree before crosslinking, is original centrifuge retention capacity after surface-crosslinked
50~95%, it is further reduced to 60~90%.The reduction degree of centrifuge retention capacity can by the type and dosage of crosslinking agent,
Reaction temperature and time adjustment.
The surface-crosslinked processing of the present invention means to increase the operation of crosslink density near particle surface.More specifically
It says, it is that by being added in molecule in particle surface there are at least two compounds of functional group that can be reacted with carboxyl to be formed
New crosslinked operation, the compound can be by forming key with the acidic group included in particulate water-absorbing resin or its reactant salt
It closes.The surface crosslinking agent that this step uses is preferably able to form covalent bond or ionic bond with water-absorbing resins surface functional group
Surface crosslinking agent.
As the surface crosslinking agent that can be used in this step, preferably for example：It is polyol compound, epoxide, more
Amine compounds or with the condensation product, oxazoline compounds of its halogenated epoxy compound, (mono-, di- or poly-) oxazoles pyridine ketone compound,
Carbonic acid alkane diester compound.It specifically includes：Polyalcohol such as polyethylene glycol, 1,2- propylene glycol, 1,3- propylene glycol, a contracting dipropyl two
Alcohol, 2,3,4- trimethyl -1,3- pentanediols, polypropylene glycol, glycerine, polyglycereol, 2- butylene-1,4-diols, 1,4- butanediols, 1,
3- butanediols, 1,5- pentanediols, 1,6-HD, 1,2- cyclohexanedimethanols etc.；Epoxide such as ethylene glycol two shrinks sweet
Oily ether, Polyethylene Glycol Bisglycidyl Ether, glycidol etc.；Multivalence amine compounds such as ethylenediamine, diethylenetriamines, triethylene
Tetramine, tetren, penten, polyethyleneimine etc.；Halogenated epoxide such as epoxychloropropane, epoxy bromine
Propane, Alpha-Methyl epoxychloropropane etc.；The condensation product of multivalence amine compounds and halogenated epoxide；Oxazolidinone compounds example
Such as 2- oxazolidones；Ring urea；Alkylene carbonate compound is such as ethylene carbonate.They can be used alone or a variety of
It is used in combination.To give full play to the effect of the present invention, it is preferable to use polyol compound and epoxide combination.As polynary
Alcohol, the preferably polyalcohol with 2~10 carbon atoms, the further preferably polyalcohol with 3~8 carbon atoms.
The dosage of surface crosslinking agent depends on using type of crosslinking agent and a combination thereof, is preferably based on water-absorbing resin 0.01
~10wt%, more preferable 0.05~5wt%.
In the present invention is surface-crosslinked, use of water is preferred for the solvent of surface crosslinking agent.The dosage of water depends on surface-crosslinked
The water content of agent effective ingredient consumption and water-absorbing resin, is preferably based on water-absorbing resin 0.2~20wt%, more preferable 0.3~
15wt%, further preferred 0.5~10wt%.In addition, hydrophilic organic solvent can be used to be used in mixed way with water, it is hydrophilic when using
Property organic solvent when, preferable organic solvent dosage be based on 0~10wt% of water-absorbing resin, more preferable 0~8wt%, further preferred 0
~5wt%.
It is preferred that surface crosslinking agent is pre-mixed in water and/or hydrophilic organic solvent, then to by treatment fluid spraying or
It is added dropwise to water-absorbing resin, more preferable spray method.The mean droplet size of the spraying is preferably 0.1~500 micron, more preferably
0.1~200 micron.
After surface crosslinking agent is added to water-absorbing resin, preferably it is heat-treated.It is 100~220 to be surface-treated temperature
DEG C, preferably 130~210 DEG C, further preferred 160~200 DEG C, heating time is preferably 1 minute~2 hours.
1.7 chelating agent
By adding in chelating agent, the time course point derived from component in urine with the water absorbing agent of Fe ionic reactions can inhibit
Solution, equally can inhibit the dissolving of water absorbing agent, reduces the absorptivity of water absorbing agent, reduce the permeability for liquids of water absorbing agent.Chelating agent exists
It is added in selected from following one or more times：(1) during polymerization；(2) after polymerisation with it is surface-crosslinked before；(3) exist
Surface-crosslinked period；(4) during agglomeration.
Chelating agent for water absorbing agent of the present invention is preferably to have high sealing ability or sequestering power to Fe or Cu ions
Chelating agent, preferably amino polyvalent carboxylic acid and its salt particularly preferably have the amino carboxylic acid and its salt of no less than 3 carboxyls.
It is 0.00001~10wt%, preferably 0.0001~1wt% that the dosage of amino polyvalent carboxylic acid, which is based on water-absorbing resin,.
1.8 inorganic powder
By adding in inorganic powder, the permeability for liquids of water-absorbing resin can be effectively promoted, preferably inorganic powder is average grain
SiO 2 powder of the diameter below 100 nanometers.The inorganic powder additive amount in terms of water-absorbing resins, be 0.001~
10wt%, preferably 0.005~1wt%, further preferred 0.01~0.5wt%.
1.9 deodorization components
Deodorant components in the present invention, preferably aldehydes can be used for the exemplary aldehyde of malodor control compositions to include but unlimited
In the clean red aldehyde (4- 2-methyl-2-phenylpropanes propionic aldehyde) of wave, lilial 33 (2- methyl -4- tert-butyl-phenyls propionic aldehyde), cinnamic acid, citral, perfume (or spice)
Leaf aldehyde, neral (dimethyl octadiene aldehyde, 3,7- dimethyl -2,6- octadiene -1- aldehyde), ligustral (Cyclal C) (2,4-
Dimethyl -3- cyclohexene-1-formaldehydes), cyanine aldehyde (3- (3- isopropyl phenyls), butyraldehyde perfume, cyclamen aldehyde (Cymal), cyclamen
Aldehyde (cyclamen aldehyde), cyclosal (Cyclosal), bitter orange aldehyde (a- methyl-cumic aldehyde
Base propyl aldehyde), methyl nonyl acetaldehyde, hydration citronellal (the light base -3,7- dimethyl-octas -1- aldehyde of 7-), helional (a- first
Base -3,4- (methylene dioxy) hydrocinnamaldehyde), hydrocinnamaldehyde (3- hydrocinnamicaldehydes, 3- hydrocinnamicaldehydes), the different hendecanal
(ten -- 10- alkene -1- aldehyde), ligustral, melonal (2,6- dimethyl -5- heptenals), methoxyl group melonal (6- methoxyl group -2,
6- dimethyl enanthaldehyde), methoxycinnamic aldehyde (trans- -4- methoxycinnamic aldehydes), Myracaldehyde (Myrac aldehyde) (isohexenyl hexamethylene
Alkenyl formaldehyde), the green aldehyde (trifernal) (3- methyl 4-phenyl propionic aldehyde, 3- phenyl butyraldehyde) of grass etc., the preferred cinnamic acid of the present invention
With cyanine aldehyde.
[2] physical property of polyacrylic acid water-absorbent resin
The polyacrylic acid water-absorbent resin of the present invention has the particulate water-absorbing agent of irregular pulverized shape, specific physical property
It is as follows.
2.1 centrifuge retention multiplying powers (CRC)
Centrifuge retention multiplying power (CRC) to the sodium-chloride water solution of 0.9wt% is preferably 10~60g/g, and more preferably 20
~55g/g, into-step preferably 25~50g/g, especially preferably 25~45g/g.For absorbability.The higher the better by CRC,
But it needs to be balanced with other physical property as the case may be in actual use.
2.2 pressurization water absorbent rates (AUP)
Water-absorbing resins are carried out surface-crosslinked to promote its water suction to the sodium-chloride water solution of 0.9wt% under stress
Multiplying power (pressurization water absorbent rate, AUP).Under 1.9kPa pressure, AUP is preferably 15~55g/g, more preferably 15~50g/g,
Into-step preferably 15~45g/g, especially preferably 15~40g/g.Under 4.8kPa pressure, AUP is preferably 10~50g/g, more
Preferably 10~45g/g, into-step preferably 10~40g/g, especially preferably 10~35g/g.The higher the better by AUP, but actually makes
Used time needs are balanced as the case may be with other physical property.
2.3 swirl method infiltration rates
The swirl method infiltration rate of water-absorbing resins of the present invention is shorter than 60sec/g, preferably 1~55sec/g, more preferable 2~
45sec/g.Water absorbing agent of the infiltration rate more than 60sec/g may not achieve the effect that enough.
[3] purposes of polyacrylic acid water-absorbent resin
The application of particle-shape water-absorbing resin of the present invention is not particularly limited, and be can be used for paper diaper, physiological hygiene cotton, is lost
Prohibit the absorbent commodities such as protection pad, be preferred for for example thin absorbing articles of thin absorption base and absorbing articles.
In absorbent commodity ,-as contain other absorbent materials (paper pulp fiber etc.), the wherein content of water-absorbing resins
It is preferably 60~100wt% into-step for 30~100wt%, preferably 40~100wt%, more preferably 50~100wt%.
[4] embodiment
The present invention will be illustrated with following embodiment and comparing embodiment, but the present invention is not limited to following embodiments.
The various performances of water-absorbing resins are measured through following methods.It is outer unless specified otherwise, water-absorbing resin, water absorbing agent and absorption
Article uses under conditions of 25 ± 2 DEG C and 50%RH (relative humidity).Used normal saline solution is the chlorine of 0.90wt%
Change sodium water solution.
4.1 centrifuge retention multiplying powers (CRC)
Centrifuge retention multiplying power (CRC) is represented under no pressurization to 0.90wt% sodium-chloride water solutions (also referred to as physiological saline
Water) water absorbent rate that is centrifuged after water suction 30 minutes.
0.20g water-absorbing resins are weighed, record weight is W0(g), it is uniformly put into the cloth made of supatex fabric
In bag, sealing is immersed in normal saline solution of the control at 25 ± 2 DEG C.After 30 minutes by the bag containing water-absorbing resins from
It is taken out in saline solution.It is dehydrated 3 minutes under 250G using centrifuge, then weighs to obtain weight W2(g).Without using any
The weight W of bag is measured after the similar operations of water absorbing agent1(g).Centrifuge retention multiplying power (g/g) is calculated according to the following formula.
Centrifuge retention multiplying power (g/g)=((W2(g)-W1(g))/W0(g))-1
4.2 pressurization water absorbent rates (AUP)
Load weighted sample is laid on filter screen ,-the bottom of a special cylinder is covered, begins to use uniform pressure
(1.9kPa/0.3psi) is applied in test sample, then cylinder is placed in-a culture dish filled with sodium chloride solution in.Sample
After product absorb 1 hour, cylinder is taken out, test absorbs amount of liquid, specific as follows：
0.900g water-absorbing resins are weighed, record weight is W3(g), it is laid in dry plexiglass cylinder strainer
On, it is uniformly distributed it.Piston is placed on cylinder, and weighs the weight of a whole set of cylinder, is recorded as W4(g).Filter plate is put
It puts in culture dish, 120 ml NaCls is added in, so that liquid surface floods surface of aluminum plate.Circular filter paper is put into filter
On plate, with sodium chloride solution complete wetting, surface is avoided to have bubble generation.A whole set of drum equipment is placed on to the filter soaked
On paper, after placing 1 hour, sample is allowed to fully absorb sodium chloride solution.Lift complete equipment and remove its piston, weigh circle again
Cylinder device is recorded as W5(g).Pressurization water absorbent rate (AUP) is calculated according to the following formula.
Pressurize water absorbent rate (g/g)=(W5(g)-W4(g))/W3(g)
4.3 swirl method infiltration rates
In 100 milliliters of beakers with stirrer, 50 ml NaCls are added in pipette, beaker is placed on magnetic
It on power blender, is stirred with 500 ± 50r/min rotating speeds, confirms that liquid level generates and stablize whirlpool.Accurately weigh 2.000 grams of water imbibitions
Resin is added in whirlpool, while starts timing with stopwatch, when liquid surface vortex disappears, and liquid level becomes horizontality, as
Terminal records the time.
4.4 deodoriging properties
Test fluid is prepared
Fermentation urine
Crude urine is collected：Freshly voided urine (Male urine in 6h, and ensuring more than initial 3 grades of grades of stink), in order to ensure
The representativeness of sample at least needs the mixed liquor of three people and three people's more than urines.
Fermentation condition：37 DEG C, in 55RH% climatic chambers, 16h.
One pack system substitutes the preparation of urine
Take laboratory physiological saline (now with the current suggest be configured with Quality Mgmt Dept physiological saline) be placed in 37 DEG C of baking ovens or
In person's thermostat water bath, heat preservation is until solution temperature is 37 DEG C.
It is taken in the conical flask of n-butylamine 0.1g to 100ml with-secondary property syringe, is settled to 50g with 37 DEG C of physiological saline, adds
Enter stirrer, sealed with preservative film, as 3min is stirred on magnetic stirring apparatus, is then placed into 37 DEG C of baking ovens or thermostatted water
In bath, 15min is kept the temperature.
It is taken in the conical flask of n-butyl mercaptan 0.005g to 100ml with-secondary property syringe, is settled to 37 DEG C of physiological saline
50g, add in stirrer, sealed with preservative film, as 3min is stirred on magnetic stirring apparatus, be then placed into 37 DEG C of baking ovens or
In thermostat water bath, 15min is kept the temperature.
Deodorization detects
SAP test methods：
The SAP for weighing 1.000 ± 0.0050 is placed in the special capsule of deodorization (confirmation before experiment, it is different whether experiment box has
Taste), freshly voided urine 25g is rapidly added thereto, and sealing immediately (pays attention to：This process allows SAP to absorb urine naturally without mixing
Liquid, it is therefore an objective to simulate actual use situations of the SAP in paper diaper).
It is positioned over 37 DEG C, in 55RH% climatic chambers, sensory evaluation is carried out after 30min.
Paper diaper are tested
Paper diaper are divided into 4 sections (being adjusted again with specific reference to paper diaper specification), are stayed with spare, comparative sample selections-sample, it will
Paper diaper are put into seal box.Using intermediate site liquid feeding, pouring into urine rapidly, (liquid feeding mode need to discuss again and urine additive amount
Need to be determined according to specific), it seals immediately, is positioned over 37 DEG C, in 55RH% climatic chambers, sense organ is carried out after 30min and is commented
Estimate.
Stink is assessed
Tester opens sample lid, and nose is gently fanned apart from bottleneck 5cm, and with hand, hears stink degree, and recorder
Member's record, each sample terminate sealing from lid is opened to detection, and 30s is not to be exceeded in the time.
Evaluation criteria is as follows：
5：Strong odor；4：Very big stink；3：It is easy to perceptible stink；2：(be able to know that is very light stink
Which kind of stink)；1：Faint stink (presence that this stink can be perceived)；0：There is no smell.
Production Example 1
By pipeline acrylic acid/sodium acrylate mixed monomer solution, (acrylic acid/sodium acrylate molar ratio is 2.2/
7.8), acrylic acid/sodium acrylate monomer concentration is 44.0wt%, and monomer solution flow is 8689kg/h.Monomer solution temperature is
80~90 DEG C.Polyethyleneglycol diacrylate (the molecule of a concentration of 11.3wt% is delivered at monomer solution pipeline branch mouth
It measures 522), flow 72kg/h.It is in addition, water-soluble by the azo-bis-isobutyrate hydrochloride that delivery pump melting concn is 6.17wt%
The sodium persulfate aqueous solution (flow 60kg/h) of liquid (flow 50kg/h) and a concentration of 4wt% forms initiator mixing turbid, and
The mixing turbid is delivered to by monomer solution pipeline branch mouth in monomer, carries out polymerisation.Reaction solution is sprayed onto reaction bed, shape
Into monomer solution (the suspended particulate grain size containing suspended particulate<100 microns, in 80~90 DEG C of monomer solutions, in 1 minute
Insoluble, meltage is less than 0.01wt%), temperature of reaction system increases rapidly, and temperature change is 90~150 DEG C, and foaming agent exists
It is decomposed under the temperature condition, obtains porous structure aqueous gel shaped polymer.
Then, aqueous gel shaped polymer is crushed, makes its grain size below 10 millimeters.And gel particle is sprawled
It is dried on a wire mesh, obtains cross linked porous structural polymer.Porous crosslinked polymeric after drying is ground carefully
Granulation, and sieved, the water-absorbent besin particles 1 with specified particle diameter are obtained,
By above-mentioned 100 parts by weight water-absorbent besin particles and 0.736 parts by weight include 1,2- propylene glycol, 1,4- butanediols,
Ethylene glycol diglycidylether and water (weight ratio 12.4:7.4:0.9:79.3) blending surface cross-linking agent solution is mixed
It closes, and surface treatment 50 minutes is carried out at 165 DEG C, obtain water-absorbing resins.
By the above-mentioned 100 parts by weight water-absorbing resins aluminum sulfate solution with a concentration of 10.3wt% of 1.317 parts by weight respectively
And 0.184 parts by weight of silica (grain size is less than 100 nanometers) powder is mixed, and obtains water absorbency resin composition A,
Embodiment 1
Reference sample 1：
Reference sample used is only to the pure water of powders A addition equivalent.
Embodiment 2:
100g powders As is taken to be placed in the three-necked flask of 250ml, then three-neck flask is placed on high speed machine blender,
Rotating speed is adjusted to the N that 200r/s sprays with spray bottle 1g 10wt% thereto, N mono- phthaloylamino peroxy caproic acid (PAP) water
Rotating speed is adjusted to 400r/s mixing and is homogenized about 10min with overhead by solution.
Embodiment 3:
100g powders As is taken to be placed in the three-necked flask of 250ml, then three-neck flask is placed on high speed machine blender,
Rotating speed is adjusted to the N that 200r/s sprays with spray bottle 2g 10wt% thereto, N mono- phthaloylamino peroxy caproic acid (PAP) water
Rotating speed is adjusted to 400r/s mixing and is homogenized about 10min with overhead by solution.
SAP Performance Evaluations such as table 2
Table 2
Remarks：5：Strong odor；4：Very big stink；3：It is easy to perceptible stink；2：Very light stink (can be known
Which kind of stink road is)；1：Faint stink (presence that this stink can be perceived)；0：There is no smell.
Claims (5)
1. a kind of super absorbent resin containing acid deodoriging properties, which is characterized in that it includes：
(a) deodorant：In acidity, in specific acid condition (pH<6.7) property is stablized under, more quick to the pH responses of environment
Sense, is the solution of solid granulates or powder or solvent or pure liquid, the deodorant volatile performance
Weak, the remaining time in super absorbent resin is long, and the additive amount based on super absorbent resin is 0.05-1wt%；
(b) unsaturated acrylic monomer,
(c) crosslinking agent.
2. the super absorbent resin according to claim 1 containing acid deodoriging properties, which is characterized in that described unsaturated third
Water soluble salt mixed solution as principal component of the aqueous solution of olefin(e) acid system monomer and crosslinking agent for acrylic acid and/or acrylic acid.
3. the super absorbent resin according to claim 2 containing acid deodoriging properties, which is characterized in that the crosslinking agent choosing
From N, N '-methylene-bisacrylamide, trimethylolpropane tris (methyl) acrylate, ethylene glycol two (methyl) acrylate,
Polyethyleneglycol diacrylate, polyethylene glycol two (methyl) acrylate, polyethylene glycol diallyl ether, pentaerythrite tetrapropylene
It is acid esters, triarylamine, ethylene glycol diglycidylether, ethylene glycol, 1,2- propylene glycol, 1,3- propylene glycol, 1,4- butanediols, sweet
It is one or more in oil, pentaerythrite, polyethylene glycol and ethylene carbonate, preferred trimethylolpropane tris (methyl) acrylic acid
It is one or more in ester, polyethyleneglycol diacrylate, ethylene glycol diglycidylether, polyethylene glycol, 1,4-butanediol, into
In the preferred trimethylolpropane tris of one step (methyl) acrylate, polyethyleneglycol diacrylate, ethylene glycol diglycidylether
It is one or more.
4. the super absorbent resin according to claim 3 containing acid deodoriging properties, which is characterized in that the deodorization ingredient
One or more in following component, the peroxy acid of alkyl and aryl, benzylhydroperoxide and cyclosubstituted benzylhydroperoxide are derived from, for mistake
Oxygen-a- naphthoic acids, a peroxide acyl sour (magnesium salts hexahydrate), carboxyl benzamide peroxy caproic acid (sodium salt), peroxide lauric acid, peroxide
Stearic acid, mono- pelargonamide peroxy caproic acids (NAPCA) of N, N, N- (3 one octyl succinyl) aminoperoxycaproic acid (SAPA) and N, N mono-
Phthaloylamino peroxy caproic acid (PAP)；With any one in amide peracid.
5. the super absorbent resin according to claim 1 containing acid deodoriging properties, which is characterized in that the combination is in height
It is added after water-absorbing resins are surface-crosslinked.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711416581.7A CN108192014A (en) | 2017-12-25 | 2017-12-25 | Super absorbent resin containing acid deodoriging properties |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711416581.7A CN108192014A (en) | 2017-12-25 | 2017-12-25 | Super absorbent resin containing acid deodoriging properties |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108192014A true CN108192014A (en) | 2018-06-22 |
Family
ID=62583730
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711416581.7A Pending CN108192014A (en) | 2017-12-25 | 2017-12-25 | Super absorbent resin containing acid deodoriging properties |
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| Country | Link |
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| CN (1) | CN108192014A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112811787A (en) * | 2021-01-15 | 2021-05-18 | 武汉美佳源环境工程有限公司 | Feces curing agent and preparation method thereof |
| JP7128978B1 (en) | 2022-03-30 | 2022-08-31 | Ｓｄｐグローバル株式会社 | Method for producing water absorbent resin composition, water absorbent resin composition, absorbent body using the same, and absorbent article |
| CN116328013A (en) * | 2023-03-27 | 2023-06-27 | 浙江卫星新材料科技有限公司 | A kind of paper diaper containing superabsorbent resin |
-
2017
- 2017-12-25 CN CN201711416581.7A patent/CN108192014A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112811787A (en) * | 2021-01-15 | 2021-05-18 | 武汉美佳源环境工程有限公司 | Feces curing agent and preparation method thereof |
| JP7128978B1 (en) | 2022-03-30 | 2022-08-31 | Ｓｄｐグローバル株式会社 | Method for producing water absorbent resin composition, water absorbent resin composition, absorbent body using the same, and absorbent article |
| JP2023147658A (en) * | 2022-03-30 | 2023-10-13 | Ｓｄｐグローバル株式会社 | Method of manufacturing water-absorbent resin composition, water-absorbent resin composition, absorber using the same, and absorbent article |
| CN116328013A (en) * | 2023-03-27 | 2023-06-27 | 浙江卫星新材料科技有限公司 | A kind of paper diaper containing superabsorbent resin |
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