CN1048422C - Modified water-absorbent besin particles - Google Patents

Modified water-absorbent besin particles Download PDF

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Publication number
CN1048422C
CN1048422C CN95190523A CN95190523A CN1048422C CN 1048422 C CN1048422 C CN 1048422C CN 95190523 A CN95190523 A CN 95190523A CN 95190523 A CN95190523 A CN 95190523A CN 1048422 C CN1048422 C CN 1048422C
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water
absorbent resin
absorbent
besin particles
particle
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CN1129407A (en
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伊达雅志
藤田正久
住谷隆
小池政法
田中健治
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Sanyo Chemical Industries Ltd
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Sanyo Chemical Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/124—Treatment for improving the free-flowing characteristics
    • 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
    • A61L15/26—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives 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
    • A61L15/42—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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    • B01J20/26—Synthetic macromolecular compounds
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    • B01J20/3206—Organic carriers, supports or substrates
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Abstract

Modified water-absorbent resin particles produced by treating particles of a substantially water-insoluble water-absorbent resin comprising a cross-linked polymer of an ethylenically unsaturated monomer containing acrylic acid and/or acrylate salt as the principal constituent with an organopolysiloxane which is liquid at ordinary temperature, wherein: 1) components (A) and (B) are in a state mixed or reacted with each other; (2) at least 95 wt.% of the particles of component (A) have diameters of 10-1,000 um; (3) the weight ratio of component (A) to component (B) is 100/(0.001-5). As compared with conventional water-absorbent resins, the invention resin particles are improved in blocking resistance after moisture absorption and prevention of dusting, absorption under normal pressure, absorption under applied pressure, and surface dryness after moisture absorption and at least retain the absorption characteristics of water-absorbent resins. Therefore the particles are suitable for various uses wherein water-absorbent resin particles are utilized, especially for hygienic articles, such as paper diaper, sanitary napkin and pad for incontinence, and absorbent patch.

Description

The water-absorbent besin particles of modification
Technical field
The present invention relates to water-absorbent besin particles with the organopolysiloxane processing.In more detail, relate to liquid organopolysiloxane and handle the few water-absorbent besin particles of problem that a kind of like this absorption rate of water-absorbent besin particles of modification improves and lumps because of moisture absorption.
Background technology
Absorbent resin has been widely used in sanitary materials such as physiological articles, paper nappy, water-loss reducer of soil etc.As the example of such absorbent resin, in fact water-fast cross-linked polymer such as the corrective of the known hydrolysate that polyacrylate cross-linking agent, self-cross linking type polyacrylate, starch-acrylate graft copolymerization body cross-linking agent, vinyl alcohol-acrylate interpolymer cross-linking agent, acrylamide interpolymer cross-linking agent arranged, cross-linked isobutylene-maleic anhydride interpolymer, carboxymethyl cellulose salt cross-linking agent.
But, though absorbent resin in the past has high absorbent capacity, but very not satisfactory on purposes such as the paper nappy that need to be used to rapid absorption speed, physiological articles, generally be that the filamentary materials such as paper pulp that particle-shape water-absorbing resin and absorption rate is fast are used in combination.
In other words, if improve the receptivity of absorbent resin, then owing to improve highly more, just strong more with the avidity of water, when resin particle contacts with water, meeting is in contact part generation gelation, thereby obstruction water the slack-off on the contrary such problem of absorption rate consequently occurred to the granule interior uniformly penetrating.
In order to improve this shortcoming, once attempted in the past to do the particle of absorbent resin very carefully increasing surface-area, improve absorption rate by the contact area that increases with water.By increasing surface-area, absorption rate slightly improves.But the part that contacts with water on the resin particle surface is formed epithelium owing to repelling, and then makes between the particle adhesion each other, impairs the uniformly penetrating of water, thereby only particle is run business into particular one to improve with absorption rate in essence and not the least concerned.
Except that above problem, when no matter water-absorbent besin particles in the past preserves resin because of its high-hygroscopicity under high humidity or in to maker feed processes such as paper nappys, the capital causes that the resin particle of moisture absorption is bonded to one another and is attached to mechanically, because this moisture absorption caking, thereby there is absorbent resin not discharge or can not be from funnel continuously and quantitatively to problems such as mechanical feed.
As the method for improving this moisture absorption anti-caking, 1. existing in the past people has proposed following～method shown in 4..
1. in water-absorbent besin particles, mix below the median size 0.05 μ m, specific surface area 50m 2The method (spy opens clear 56-133028 communique) of the micronized hydrophobic silica that/g is above.
2. in water-absorbent besin particles, add the method (spy opens clear 59-80459 communique) of inorganic powders such as aqueous silicon dioxide, aqueous alumina, oxidizing aqueous titanium.
3. water-absorbent besin particles is handled the method (spy opens clear 61-69854 communique) of afterwards, further adding high-melting-point organic compound powder with cationic surfactant.
4. mix stearic acid and inorganic powder in the water-absorbent besin particles, make resin surface cover the stearic method of one deck (spy opens clear 63-105064 communique).
Yet, in above-mentioned method 1., the interpolation of hydrophobic silica is to improve the moisture absorption anti-caking, but because hydrophobic silica has covered the resin particle surface, absorption rate, add the initial stage absorbed dose depressed and absorb multiplying power and all can descend, moreover because admixed finepowder shape silicon-dioxide also has problems such as a large amount of dust of generation.
In above-mentioned method 2., do not have under the hydrophobic situation at inorganic powder, it is not too large with the decline degree that absorbs multiplying power to add the initial stage absorbed dose of depressing, but the improvement of moisture absorption anti-caking is not remarkable, and because inorganic powder is little powdered, with above-mentioned 1. identical, the problem that produces a large amount of dust is arranged also.And have under the hydrophobic situation at inorganic powder, have and above-mentioned 1. same problem.
With regard to 3. above-mentioned and 4. method, because hydrophobic, high melting point organic compound or stearic acid have covered the surface of resin particle, the possibility of improving the moisture absorption anti-caking to a certain extent is not too big, and, because high melting-point organic compound or stearic acid have hindered the absorptivity of absorbent resin, also have to add the initial stage absorbed dose of depressing or absorb the problem that multiplying power descends.
Therefore, first purpose of the present invention is by the water-absorbent besin particles modification, promotes water, urine, menses etc. to the inner uniformly penetrating of water-absorbent besin particles, thereby the water-absorbent besin particles with high absorption rate is provided.
In addition, second purpose of the present invention is by the water-absorbent besin particles modification, eliminate 1. above-mentioned～problem of 4. waiting the moisture absorption anti-caking to exist in improving one's methods, thus provide moisture absorption caking rate and dust degree low, add initial stage absorbed dose of depressing and the water-absorbent besin particles that absorbs the multiplying power excellence.
Disclosure of the Invention
The invention provides the water-absorbent besin particles of modification, it is characterized in that, it is to be that the particle of a kind of so water-fast in fact absorbent resin of crosslinked polymer (A) of the unitary ethylenically unsaturated monomers of main structure is handled the modified water absorbent resin particle that forms with the organopolysiloxane (B) that is in a liquid state at normal temperatures with vinylformic acid and/or acrylate, wherein
1. (A) and (B) be and mix and/or response behaviour,
2. in the particle of (A), the granule content of 10～1,000 μ m accounts for more than 95% (weight),
3. the weight ratio of (A)/(B) is 100/ (0.001～3).
In other words, present inventor's modified water absorbent resin particle is that this absorbent resin (A) forms with this organopolysiloxane (B) processing modification, by this processing, (A) particle surface or be the state that (B) adheres to is perhaps owing to (A) being state on the particle surface that (B) anchor at (A) with (B) reaction.Because of (A) with (B) have anergy different, or be admixture, or be response behaviour.
No matter be in any state, (A) the particulate surface is owing to use liquid organopolysiloxane (B) modification, thereby also invested wettability in the moisture absorption anti-caking of modified water absorbent resin particle of the present invention under improving high humidity, thereby prevent the generation of dust.
In addition, the bonded to one another and shortcoming of uniformly penetrating of infringement water between the sort of water-absorbent besin particles of prior art, also the modified effect owing to (B) among the present invention improves, thereby has improved absorption rate.
And then present inventor's modified water absorbent resin particle is adding the initial stage absorbed dose depressed and is absorbing aspect the multiplying power also very excellent.
Preferred forms of the present invention
In the present invention, this absorbent resin (A) is can absorb a large amount of water when contacting with water and swelling and form the water-fast in fact resin of aqueous gel shape thing (hydrogel).And this absorbent resin (A) is to be that main structure is unitary, the crosslinked polymer of ethylenically unsaturated monomers with vinylformic acid and/or acrylate.
As such absorbent resin (A), for example, can enumerate the crosslinked body of polyacrylic acid part corrective, self-cross linking type polyacrylic acid part corrective, starch-acrylate graft copolymerization body cross-linking agent, the hydrolysate of starch-acrylonitrile graft copolymer body, vinyl alcohol-acrylate interpolymer cross-linking agent, the hydrolysate of acrylate-acrylamide interpolymer cross-linking agent, the hydrolysate of acrylate-acrylonitrile compolymer body cross-linking agent, the interpolymer cross-linking agent of acrylate and 2-acrylamide-2-methyl propane sulfonic acid salt, the corrective of cross-linked isobutylene-maleic anhydride interpolymer, and be used in combination in the middle of these.
In addition, above-mentioned as this absorbent resin (A) and illustrational various cross-linked polymer is a raw material with carboxylate salts such as acrylate, and under the such salify situation of corrective or part corrective,, can use sodium salt, sylvite, ammonium salt, amine salt etc. as salt.Be preferably sodium salt and sylvite.
Like this some as the illustrational material of this absorbent resin (A) in, if the absorption characteristic when considering finally to use as absorbent resin, then be preferably the crosslinked body of polyacrylic acid part corrective, self-cross linking type polyacrylic acid part corrective, starch-acrylate graft copolymerization body cross-linking agent, and vinyl alcohol-acrylate interpolymer cross-linking agent.
This absorbent resin (A) better use under normal pressure to the absorptive character of normal saline solution (0.9% sodium chloride aqueous solution) normally conduct oneself with dignity more than 30 times, be more preferably 35～80 times, good especially be 40～70 times resin.
Particulate size-grade distribution about this absorbent resin (A), must use size-grade distribution is particle diameter 10～1 in (A) particle, the granule content of 000 μ m accounts for the above water-absorbent besin particles of 95% (weight), and better being to use size-grade distribution is that the granule content of particle diameter 50～850 μ m accounts for the above water-absorbent besin particles of 95% (weight).For size-grade distribution is particle diameter 10～1, the water-absorbent besin particles of the granule content less than 95% (weight) of 000 μ m under the situation of the water-absorbent besin particles that uses size-grade distribution partly to occupy the majority as small particle size, is repelled during suction easily, absorption rate reduces, thereby bad.On the other hand, be that the suction that arrives granule interior during suction needs the time, thereby absorption rate is reduced, and is also bad under the situation of the water-absorbent besin particles that partly occupies the majority of big particle diameter using size-grade distribution.Median size is not particularly limited, but better is 200～600 μ m.
The particle shape of this absorbent resin (A) is not particularly limited, different because of method for making, can comprise the pearl that obtains with the anti-phase suspension polymerization, the flakey that obtains with the drum dried method, resin mass is pulverized rock-like or the amorphous that obtains, and the granulation thing of these particles.
This organopolysiloxane (B) can be to be in a liquid state at normal temperatures among the present invention, and can also be have reactivity or responding property with this absorbent resin (A).That is, as (B), can enumerate does not have reactive and responding property to carboxylic acid (salt) base in this absorbent resin (A).(the what is called here " carboxylic acid (salt) base " means carboxylic acid group and/or carboxylate group, down together).In this case, the organosilane monomer that is commonly referred to as silane coupling agent is the lower monomer of molecular weight ratio, owing to only can not reach being mixed into the purpose effect, thereby be not suitable as this organopolysiloxane (B).
In the middle of (B), reactive as (A) do not had, can enumerate dimethyl silicone oil, methyl hydrogen silicone oil, methyl phenyl silicone oil, ring-type dimethyl silicone oil, polyethers sex change silicone oil, carboxyl sex change silicone oil, alkyl sex change silicone oil, alkoxyl group sex change silicone oil etc.These can two or more and usefulness.And these emulsion forms that emulsification forms in water also can be used for the present invention preferably.
In the middle of (B), as to (A) responding property, can enumerate the silicone oil of the functional group with at least one carboxylic acid (salt) radical reaction that can be had with (A), specifically, can enumerate amino sex change silicone oil, epoxy sex change silicone oil, methanol modified silicone oil, phenol sex change silicone oil, sulfydryl sex change silicone oil etc.
(A) do not had in reactive compound,, be preferably dimethyl silicone oil and polyethers sex change silicone oil from can obtain this point less expensively.
In the compound to (A) responding property, being preferably can be at amino sex change silicone oil and the epoxy sex change silicone oil than lower temperature and carboxylic acid (salt) radical reaction.From normal temperature just can with carboxylic acid (salt) radical reaction this point, good especially is amino sex change silicone oil.
As amino sex change silicone oil, the end and/or the intramolecularly that can be set forth in the siloxane polymer molecule have-R 1NR 2R 3Shown group (R in the formula 1It is the alkylidene group of 1～12 carbon; R 2, R 3It is the alkyl of H or 1～12 carbon.Alkylidene group and/or alkyl can have more than one hydrogen atom by OH base, COOH base, NH 2Replacements such as base; Under the situation of 2 above carbon atoms, can also contain the ehter bond that between C-C, contains Sauerstoffatom) amino sex change silicone oil etc.
As epoxy sex change silicone oil, the end and/or the intramolecularly that can be set forth in the siloxane polymer molecule have-and (R is the alkylidene group of 1～12 carbon to the group shown in the RX in the formula; X is an epoxy group(ing).Alkylidene group can have more than one hydrogen atom by replacements such as OH base, COOH bases; Have at alkylidene group under the situation of 2 above carbon atoms, can contain the ehter bond that between C-C, contains Sauerstoffatom) epoxy sex change silicone oil etc.
In the middle of above-mentioned (B), do not having in the compound of reactive and responding property with (A), if when considering moisture absorption not with the anxiety of resin particle surface isolation, and expectation having aspect the anchorage modified effect good and consumption is few with (A), then the compound of responding property is better.
In the middle of above-mentioned (B), with the reactive functional group number of the organopolysiloxane of (A) responding property can be to have usually more than 1 in the 1 molecule silicone oil.But this functional group also has both and the crosslinked purpose of resin particle near surface, thereby 2 above persons are better.From carrying out effectively crosslinked viewpoint, better the reactive functional group number is 2～20.And functional group's position can be the end, side chain of siloxane polymer or terminal and that side chain haves both at the same time is any.
This organopolysiloxane (B) is as long as be in a liquid state just passablely at normal temperatures, and its molecular weight is not particularly limited, and better is more than 1,000, is more preferably more than 3,000.The molecular weight upper limit of this organopolysiloxane (B) is not particularly limited, and normally about 1,000,000.Owing to use the organopolysiloxane of molecular weight more than 1,000, thereby needn't worry that moisture absorption caking rate or dust degree can pass in time and worsen.
The surface tension of this organopolysiloxane (B) is not particularly limited, but better is 18～30 dyne/cm, is more preferably 20～26 dyne/cm.If use the organopolysiloxane of surface tension in above-mentioned scope, can prevent that then (B) takes place to the water-absorbent besin particles internal penetration situation that is easy to that becomes, thereby needn't use (B) in a large number for producing a desired effect, not only economy but also do not worry crossing absorptive character are descended because of anti-water effect.Do not worry producing the problem that powder flowbility is poor, the generation caking is so yet.Above surface tension is the numerical value 25 ℃ of mensuration.
(B) as long as viscosity be in a liquid state at normal temperatures just is not particularly limited, but better is 10～20,000 centistoke (unit of kinematic viscosity) Si (cst) at normal temperature (25 ℃), good especially is to dilute with solvent based, from easily with (A) blended viewpoint, be 30～1,000cst.
By using the organopolysiloxane of above-mentioned viscosity, can use low viscosity organopolysiloxane or other solvent (as methyl ethyl ketone, Cellosolve, lauryl alcohols etc.) use the dilution back, remove dilution with the processing step of solvent with needn't adding after (A) combination treatment, not only economy but also can make powder flowbility keep good, also make (B) to be difficult to be penetrated into water-absorbent besin particles inside, needn't use (B) just can produce a desired effect in a large number, thereby can not take place owing to (B) making absorption rate slack-off to the adhesive effect between the particle of (A), situations such as caking, because these reasons, it is preferably.Above viscosity is the numerical value 25 ℃ of mensuration.
The particle of this absorbent resin (A) can have various variations with the relative consumption of this organopolysiloxane (B), but (A) particle: weight ratio (B) normally 100: (0.001～5), better be 100: (0.001～3), especially 100: (0.01～1).
If ratio (B) is less than under 0.001 the situation, and is good inadequately for the effect of moisture absorption caking rate, the water absorbency resin composition of the absorption rate that just can not be improved.
On the other hand, if above 5,,, in fact be difficult to use owing to produced absorptive character decline, bad, more such other problems of generation caking of powder flowbility though the improvement of absorption rate is effectively.
In addition, the particle of this absorbent resin (A) that the present invention uses not only can be handled modification with (B), can also be at (A) particulate near surface with having of linking agent (C) the further crosslinking Treatment modification of at least 2 energy with the functional group of carboxylic acid (salt) radical reaction, water-absorbent besin particles with this modified structure is more suitable for using in the present invention because absorption rate further improves and gel-strength also increases.
With linking agent (C) particle of (A) is carried out the surface-crosslinked time and be not particularly limited, before the particle of (A) is handled with (B), with handling, carry out simultaneously or after with (B) processing, any time can with (B).
The kind of this linking agent (C) is different because of the kind of used absorbent resin (A) or the kind of organopolysiloxane (B) etc., can enumerate, for example, polyglycidyl ether compounds, many alcohol compounds, polyamine compounds, polyamines resinoid, carbonats compound, halogen epoxy compounds, many aldehyde compounds etc.
The specific examples of polyglycidyl ether compound can be enumerated, for example, and ethylene glycol diglycidylether, glycerine-1, the 3-diglycidylether, T 55, polyethyleneglycol diglycidylether, 1,6-hexanediol diglycidyl ether, Polyglycerine polyglycidyl ether etc.
The specific examples of many alkylol cpds can be enumerated, for example, and glycerine, ethylene glycol, polyoxyethylene glycol, polypropylene glycol, diethanolamine etc.
The specific examples of polyamine compounds can be enumerated, for example, and quadrol, diethylenetriamine, triethylene tetramine etc.
The resinoid specific examples of polyamines can be enumerated, for example, and multiamide polyamines epichlorohydrin resins, polyamines epichlorohydrin resins etc.
The specific examples of carbonats compound can be enumerated, for example, and ethylene carbonate etc.
The specific examples of halogen epoxy compounds can be enumerated, for example, and Epicholorohydrin, Alpha-Methyl Epicholorohydrin etc.
The specific examples of many aldehyde compounds can be enumerated, for example, and glutaraldehyde, oxalic dialdehyde etc.
In the above compound of enumerating as linking agent (C), from can be with carboxylic acid (salt) thus base forms strong covalent bond to be obtained being preferably polyglycidyl ether compounds, many alcohol compounds and polyamines resinoid in viewpoint of excellent water-absorbent besin particles all aspect absorption rate and the gel-strength two.The viewpoint low from temperature of reaction, that energy expenditure is saved money, be more preferably ethylene glycol diglycidylether, propylene glycol diglycidylether, glycerine-1,3-diglycidylether, T 55, polyamines epichlorohydrin resins and multiamide polyamines epichlorohydrin resins.
The usage quantity of above-mentioned linking agent (C) is different because of kind and degree of crosslinking, the resulting modified water absorbent resin particulate performance objective of the present invention etc. of the kind of linking agent (C), absorbent resin (A), but absorbent resin (A): the weight ratio of linking agent (C) normally 100: (0.001～5), be preferably 100: (0.001～3), especially good be 100: (0.01～2), best be 100: (0.05～1).In above-mentioned scope, use this linking agent (C), neither can reduce absorbed dose, can also further improve the absorption rate of water-absorbent besin particles, also can increase gel-strength, thereby better.
(B) [and in case of necessity and the above-mentioned linking agent (C) of usefulness] to (A) particulate addition means, so long as can add the method for institute's determined number, any method can, for example, can enumerate
A) method of the direct fusion of each composition,
B) in advance (B) added in (A) with high density (for example 5～20% weight concentrations), is mixed and made into female glue of practicing, then, amount to (B) decide addition the master batch interpolation be mixed into method in (A),
C) emulsion of (B) is added the method that is mixed in (A) particle,
D) (B) [and in case of necessity and the linking agent (C) of usefulness] is dispersed or dissolved in hydrophobicity and/or the hydrophilic organic solvent, adds the method that is mixed in (A) particle again,
E) (B) [and in case of necessity and the linking agent (C) of usefulness] dissolved or be dispersed in the mixed solvent of hydrophilic organic solvent such as alcohols and water, add the blended method again.
(B) [and in case of necessity and the linking agent (C) of usefulness] (A) particulate is added the device that uses when handling can be common mixing machine, for example, can enumerate round tube type mixing machine, spiral type mixing machine, spiral type extrusion machine, turbulizer, promise tower mixing machine, V-Mixer, spiral strip type mixing machine, two oar kneading machine, flowing-type mixing machine, airflow mixing machine, carousel-type mixing machine, taper blending machine, rolling type mixing machine etc.
Above-mentioned such mixture of obtaining handled if necessary, also can carry out to promote that reaction is the heating of purpose because of (B) [and in case of necessity and the linking agent (C) of usefulness] has or not reactive functional group and reactive different.And above-mentioned mixing and heating also can be carried out simultaneously.In addition, so-called reaction, mean " absorbent resin (A) " and " use with the sex change silicone oil of (A) responding property as the sex change silicone oil under the situation of (B) and the linking agent (C) of usefulness also in case of necessity " crosslinking reaction.
Under the situation of heating, normally 60～200 ℃ of temperature, better it is 80～180 ℃.This heating can be used drying machine or heater, and for example hot air dryer, rotary dryer, paddle dryer, collar plate shape heater, flow laminar drying machine, driving band type drying machine, the tower heater of promise, infrared heating machine etc. carry out.
In the modified water absorbent resin particle of the present invention, can add silicon-dioxide fines (D) in any stage of this modification.(D) interpolation can make absorption rate further improve.And can expect the further raising of powder flowbility.
As the example of this silicon-dioxide fines (D), can enumerate the silicon tetrachloride dry type inorganic silicon dioxide that hydrolysis is made in oxygen and hydrogen high-temp combustion flame, be referred to as " smog silicon-dioxide " (Fumed Silica) usually.Thereby also can and further react the silicon-dioxide that has imported alkyl with the silanol group that makes the inorganic silicon dioxide surface and monomethyl trichlorosilane, dimethyldichlorosilane, chlorotrimethylsilane etc.Specifically, can enumerate specific surface area 50～500m 2/ g, primary granule particle diameter are the silicon-dioxide of 5～50nm.
Silicon-dioxide fines (D) is that above-mentioned specific surface area and granularity, the so-called wetting ability silicon-dioxide of wetting ability degree more than 70% are arranged preferably.The wetting ability degree here means the weight ratio of the silicon-dioxide that suspends with colloidal in the mixed solution of water/methyl alcohol=70/30 (weight ratio).This value is more little, and hydrophobicity is just strong more, and what be commonly referred to as hydrophobic silica is that the wetting ability degree is 0% silicon-dioxide.If hydrophobicity strengthens, then also owing to, the absorption rate of water-absorbent besin particles is had a declining tendency, thereby better use the wetting ability silicon-dioxide of wetting ability degree more than 70% (B) with respect to the addition of (A).
Under the situation of using silicon-dioxide fines (D), its quantity better is 0.01～1% (weight) with respect to the quantity of (A) 0.001～2% (weight) normally.Be more preferably the relative addition amount still less to (A) than (B).Be in above-mentioned scope by the addition that makes (D), can further improve absorption rate, both do not had poplar dirt problem, but also the phase is waitd upon the raising of powder flowbility.
Adding the method for silicon-dioxide fines (D) can enumerate, for example, in (A) particle, add the method for mixing (D) in advance, in (B), add the method for mixing (D), the method of adding (D) simultaneously at (A) particle and (B) blended is added the method for mixing (D) etc. in the mixture of (A) particle and (B).
In the modified water absorbent resin particle of the present invention, in the scope of not damaging effect of the present invention, can cooperate organic dust (for example paper pulp powder, derivatived cellulose, natural polysaecharides etc.) as extender or additive, inorganic powder (for example zeolite, silicon-dioxide, aluminum oxide, wilkinite, gac etc.), oxidation inhibitor, sanitas, sterilant, tensio-active agent, tinting material, spices, reodorant etc. in case of necessity, these amount of substances for modified water absorbent resin particulate weight usually below 10% (weight).
Modified water absorbent resin particle of the present invention is water-fast in fact resin particle, its moisture absorption caking rate, dust degree, absorption characteristic can be controlled according to application target, but 1. under the high humidity (40%, 80%RH, after 3 hours) the moisture absorption caking rate usually below 20%, below 10%, 2. the dust degree is usually below 10cpm more fortunately, more fortunately below the 5cpm, 3. adding of normal saline solution, depressed the initial stage absorbed dose more than the 20g/g, more fortunately more than the 25g/g.The upper limit of initial stage absorbed dose is not particularly limited, is the bigger the better, but usually below 50g/g.
So-called normal saline solution means sodium chloride aqueous solution (concentration 0.85～0.95% (weight)).
Therefore, modified water absorbent resin particle of the present invention, even the moisture absorption caking also takes place under the situation about using under high humidity hardly, dust also takes place when being made into paper nappy hardly, and owing to add the initial stage absorbed dose excellence of depressing, gel drying sense after the suction is good, gives dry and comfortable sensation.Therefore, for example, using loads such as can tolerating infant weight under the situation of paper nappy etc., absorb a large amount of urines simultaneously rapidly, the dry sensation on the paper nappy surface, back of urinating is good.
Below further specify the present invention, but the present invention is not limited by these examples with embodiment and comparative example.
Embodiment 1～4, comparative example 1～7
Moisture absorption caking rate in embodiment 1～4, the comparative example 1～7, dust degree, add the initial stage absorbed dose of depressing and add the absorption multiplying power of depressing and adopt following method to measure.Below be not particularly limited, % represents weight %.
The moisture absorption caking rate:
The water-absorbent besin particles of the following granularity of 10g 840 μ m is evenly put in the aluminum ware of 5cm diameter, places 3 hours in 40 ℃, the climatic chamber of relative humidity 80%.Water-absorbent besin particles after the placement sieves lightly with 12 orders (JIS Z8801, JIS is this industrial standards in a few days, has 1410 μ m sieve apertures) wire netting, measures because of the moisture absorption caking becomes weight resin more than the 1410 μ m, obtains the moisture absorption caking rate by following formula.
Moisture absorption caking rate (%)
=(the resin particle gross weight after the weight resin/placement more than the 1410 μ m) * 100
The dust degree:
The thief hatch of the suction port of 1L suction bottle and digital dust gauge (bavin field section length of schooling) is connected with the Glass tubing of internal diameter 7mm, long 10cm.Suitable for reading from suction bottle, fall into suction bottle with funnel by the 20g water-absorbent besin particles.The dust number that the water-absorbent besin particles that falls with digital dust gauge mensuration produced in 1 minute is worth this as dust degree (cpm of unit, the i.e. number of per minute).
Add the initial stage absorbed dose of depressing and absorb multiplying power:
Post in the bottom surface in the cylindric plastics tubing (internal diameter 30mm, height 60mm) of 250 orders (having 63 μ m sieve apertures) nylon wire and put the 0.1g water-absorbent besin particles into, evenly spread out, on this resin particle, add the counterweight of external diameter 30mm, make it to reach 20g/cm 2Load.
The plastics tubing of the water-absorbent besin particles of having packed into is immersed the ware (diameter: 12cm), place that fills the 60ml normal saline solution down with the nylon wire side.Measure water-absorbent besin particles after 10 minutes and after 60 minutes because of absorbing the weight that normal saline solution increases.10 times of values of gaining in weight after 10 minutes are as depressing the initial stage absorbed dose to adding of normal saline solution, and 10 times of values of gaining in weight after 60 minutes are as the absorbent rate under pressure to normal saline solution.
Embodiment 1
The commercially available particle-shape water-absorbing resin of 100g " サ Application ウ エ Star ト IM-5000 D " [crosslinked polypropylene acid moieties sodium neutralized salt, Sanyo changes into industry (strain) system; Particle diameter 10～1, the granule content of 000 μ m account for more than 99.9% (weight)] put in the polyethylene bag, in this bag, add the amino sex change silicone oil of 0.2g [SHIN-ETSU HANTOTAI's chemical industry (strain) system, " KF-880 " (surface tension 21.3 dyne/cm; Viscosity 650cps; Molecular-weight average about 20,000)], thorough mixing obtains modified water absorbent resin particle of the present invention (a1).The results are shown in Table 1 in the performance measurement of this product.
Embodiment 2
The commercially available particle-shape water-absorbing resin of 100g " サ Application ウ エ Star ト IM-5800 " [the surface-crosslinked product of crosslinked polypropylene acid moieties sodium neutralized salt, Sanyo changes into industry (strain) system; Particle diameter 10～1, the granule content of 000 μ m accounts for more than 99.9% (weight)] capacity of putting into is constantly to stir in ジ ユ-サ-mixing machine of 2000ml, add 0.5g epoxy sex change silicone oil [SHIN-ETSU HANTOTAI's chemical industry (strain) system, " KF-101 " (surface tension 25.2 dyne/cm simultaneously; Viscosity 2,000cps; Molecular-weight average about 9,000)], thorough mixing.The mixture that obtains obtains modified water absorbent resin particle of the present invention (a2) about 20 minutes of 150 ℃ of heat treated.The results are shown in Table 1 in the performance measurement of this product.
Embodiment 3
The commercially available particle-shape water-absorbing resin of 100g " サ Application ウ エ Star ト IM-1000 " [starch/acrylic acid-grafted polymeric part sodium neutralized salt, Sanyo changes into industry (strain) system; Particle diameter 10～1, the granule content of 000 μ m accounts for more than 99.9% (weight)] capacity of putting into is 2, constantly stir in ジ ユ-サ-mixing machine of 000ml, be added on simultaneously and dissolved 6% (weight) epoxy sex change silicone oil [SHIN-ETSU HANTOTAI's chemical industry (strain) system in 80% (weight) methanol aqueous solution, " KF-101 "] and 2% (weight) ethylene glycol diglycidylether [Na ガ セ changes into industry (strain) system, " デ Na コ-Le EX-810 "] methanol aqueous solution 5g (for 100 parts of water-absorbent besin particles, be equivalent to 0.3 part " KF-101 " and 0.1 part " EX-810 " respectively), thorough mixing.The mixture that obtains obtains modified water absorbent resin particle of the present invention (a3) about 20 minutes of 150 ℃ of heat treated.The results are shown in Table 1 in the performance measurement of this product.
Embodiment 4
100g " サ Application ウ エ Star ト IM-1000 " is put into capacity 2, constantly stir in ジ ユ-サ-mixing machine of 000ml, add 0.1g epoxy sex change silicone oil [SHIN-ETSU HANTOTAI's chemical industry (strain) system, " X-22-163B " (surface tension 21.0 dyne/cm simultaneously; Viscosity 65cps; Molecular-weight average about 3,000)], with in 30% (weight) aqueous solution of 3 moles of ethylene oxide affixtures of methyl alcohol, dissolved the aqueous solution 5g of 6% (weight) polyamines epichlorohydrin resins (for 100 parts of absorbent resin, be equivalent to 0.1 part " X-22-163B " and 0.3 part of polyamines epichlorohydrin resins respectively), thorough mixing.The mixture that obtains obtains modified water absorbent resin particle of the present invention (a4) 150 ℃ of heat treated 20 minutes.The results are shown in Table 1 in the performance measurement of this product.
Comparative example 1
Directly use commercially available " サ Application ウ エ Star ト IM-5000D " water-absorbent besin particles (b1) in contrast.The results are shown in Table 1 in the performance measurement of this product.
Comparative example 2
Directly use commercially available " サ Application ウ エ Star ト IM-5800 " water-absorbent besin particles (b2) in contrast.The results are shown in Table 1 in the performance measurement of this product.
Comparative example 3
Directly use commercially available " サ Application ウ エ Star ト IM-1000 " water-absorbent besin particles (b3) in contrast.The results are shown in Table 1 in the performance measurement of this product.
Comparative example 4
In the commercially available particle-shape water-absorbing resin of 100g " サ Application ウ エ Star ト IM-5000D ", add 0.5g hydrophobic silica (" ア エ ロ ジ Le-972 "), obtain contrasting water-absorbent besin particles (b4).The results are shown in Table 1 in the performance measurement of this product.
Comparative example 5
In the commercially available particle-shape water-absorbing resin of 100g " サ Application Star ウ エ Star ト IM-5000D ", add the titanium oxide of 1.0g particle diameter 30 μ m, obtain contrasting water-absorbent besin particles (b5).The results are shown in Table 1 in the performance measurement of this product.
Comparative example 6
In the commercially available particle-shape water-absorbing resin of 100g " サ Application ウ エ Star ト IM-5800 ", add the 5g dissolved Varisoft TA 100 of heating, polystyrene powder at 80 ℃ of stirrings interpolation 0.5g particle diameter 20 μ m after 10 minutes obtains contrasting water-absorbent besin particles (b6).The results are shown in Table 1 in the performance measurement of this product.
Comparative example 7
In the commercially available particle-shape water-absorbing resin of 100g " サ Application ウ エ Star ト IM-5800 ", add the 1g stearic acid, make the stearic acid fusion, stirred 10 minutes in this temperature 80 ℃ of heating.Then, to wherein adding 3g silicon-dioxide, the thorough mixing postcooling obtains contrasting water-absorbent besin particles (b7) to room temperature.The results are shown in Table 1 in the performance measurement of this product.
Table 1
Water-absorbent besin particles Moisture absorption caking rate (%) Dust degree (cpm) Add the initial stage absorbed dose of depressing (g/g) Add the absorption multiplying power of depressing (g/g)
Embodiment 1 (a1) 5 0 26 34
Embodiment 2 (a2) 3 2 31 38
Embodiment 3 (a3) 1 4 32 37
Embodiment 4 (a4) 0 2 31 36
Comparative example 1 (b1) 95 60 15 30
Comparative example 2 (b2) 90 50 24 35
Comparative example 3 (b3) 98 70 3 10
Comparative example 4 (b4) 13 210 8 21
Comparative example 5 (b5) 70 980 12 27
Comparative example 6 (b6) 40 80 14 27
Comparative example 7 (b7) 30 40 13 28
Can understand following situation from table 1:
1. modified water absorbent resin particle of the present invention (a1)～(a4) and untreated water-absorbent besin particles (b1)～(b3) relatively moisture absorption caking rate, dust degree, add the initial stage absorbed dose of depressing and absorb multiplying power tremendous improvement is all arranged.
2. modified water absorbent resin particle of the present invention (a1)～(a4) and contrast water-absorbent besin particles (b4)～(b7) relatively moisture absorption caking rate, dust degree, add the initial stage absorbed dose of depressing and absorb multiplying power and all show excellent.
3. in addition, the water-absorbent besin particles of comparative example (b4)～(b6) compares with untreated water-absorbent besin particles (b1)～(b3), though the moisture absorption caking rate makes moderate progress, the dust degree has worsened.Moreover contrast water-absorbent besin particles (b4)～(b7) compares with untreated absorbent resin (b1)～(b3) generally, adds the initial stage absorbed dose of depressing and absorb multiplying power to worsen.
Embodiment 5～16, comparative example 8～12
The normal pressure absorbed dose of the water-absorbent besin particles in embodiment 5～16 and the comparative example 8～12, pressurizing absorption amount, absorption rate, perviousness, gelation time are measured with following method.
The normal pressure absorbed dose:
(vertical: 20cm with the tea-bag that 250 orders (having 63 μ m sieve apertures) nylon wire is made; Horizontal: put into the 1g water-absorbent besin particles 10cm), dipping was mentioned after 30 minutes in 500ml normal saline solution (0.9% sodium chloride aqueous solution), and the weight that increases is measured in draining 15 minutes, is worth as the normal pressure absorbed dose with this.
The pressurizing absorption amount:
The bottom surface is posted in the cylindric plastics tubing (internal diameter 30mm, height 60mm) of 250 orders (having 63 μ m sieve apertures) nylon wire and is put into the 0.1g water-absorbent besin particles, evenly spreads out, and presses the counterweight of external diameter 30mm on this resin, makes it to reach 20g/cm 2Load.The plastics tubing that water-absorbent besin particles is housed flooded 30 minutes in the ware that fills the 60ml normal saline solution (diameter 12cm) down with the nylon wire side.With 10 times of values of the weight that increases after 30 minutes as the pressurizing absorption amount.
Absorption rate:
Putting into 50ml normal saline solution and magnetic stick in the 100ml beaker (is substantially cylindric, long 30mm, middle part diameter 8mm, two ends diameter 7mm), with magnetic stirrer magnetic stick is rotated with 600 rev/mins speed, drop into the 2.0g water-absorbent besin particles simultaneously, measure after dropping into and count the time of stopping the rotation immediately to stirrer, with this as absorption rate.
Perviousness:
In the 50ml beaker, put into the 2g water-absorbent besin particles, slowly add the 30ml normal saline solution subsequently,, judge the infiltration state of normal saline solution with visual method then to water-absorbent besin particles inside so that absorbent resin does not spread.Criterion is as follows: ◎: do not generate the thing of being ostracised, permeate well zero: permeate well, but generate some thing △ that are ostracised: perviousness is poor slightly, can think be ostracised thing generate *: poor permeability all generates the things of being ostracised
Gelation time:
In the 50ml beaker, add the 2g water-absorbent besin particles, slowly add the 30ml normal saline solution subsequently,, measure then until the whole gelations of liquid and do not have time of fluidity, be worth as gelation time with this so that absorbent resin does not spread.
Comparative example 8
Add 95g sodium acrylate, 27g vinylformic acid, 0.3g N in the glass reaction container of capacity 1L, N '-methylene diacrylamine and 430g deionized water stir, mix, and make the temperature of content remain on 5 ℃ simultaneously.Content feeds nitrogen, and dissolved oxygen content is dropped to below the 1ppm, adds 1g 1% aqueous hydrogen peroxide solution and 1g 0.3% aqueous ascorbic acid then with initiated polymerization, by polymerization in about 5 hours, obtains aqueous gel shape polymer.This aqueous gel shape polymer is ground into the following granularity of particle diameter 850 μ m 130～150 ℃ of warm air dryings, obtains water-absorbent besin particles (b8).(b8) contain the following particulate of 7.2% particle diameter, 105 μ m, and contain the following particulate of 1.0% particle diameter, 45 μ m.The results are shown in Table 2 in the performance measurement of this water-absorbent besin particles (b8).
Comparative example 9
The water-absorbent besin particles that comparative example 8 obtains (b8) 100g high-speed stirring, go up the even spraying 1g 10% ethylene glycol diglycidylether aqueous solution to (b8) simultaneously, about 140 ℃ of heat treated 30 minutes, obtain having the water-absorbent besin particles (b9) of crosslinking Treatment near surface.Though size-grade distribution (b9) is with (b8) roughly the same, the following fraction of particle of particle diameter 105 μ m is 6.4%, and the following particulate of particle diameter 45 μ m is 0.9%.In contrast, the results are shown in Table 2 in the performance measurement of this water-absorbent besin particles (b9).
Comparative example 10
Remove the following particulate of particle diameter 105 μ m in the water-absorbent besin particles that comparative example 8 obtains (b8), obtain absorbent resin (b10).The results are shown in Table 2 in the performance measurement of this water-absorbent besin particles (b10).
Comparative example 11
Pack in the glass reaction container of capacity 1L 100g vinylformic acid, 0.3g tetraene propoxy-ethane and 350g deionized water stir, and make the temperature of content remain on 5 ℃ simultaneously.Feed nitrogen in the content, make dissolved oxygen content drop to 1ppm following after, add 1g 1% aqueous hydrogen peroxide solution and 1g 0.3% aqueous ascorbic acid polymerization caused, by polymerization in about 5 hours, obtain aqueous gel shape polymer.
It is mixing that this aqueous gel shape polymer is paid extrusion machine with the order ware, adds 116g 35% aqueous sodium hydroxide solution simultaneously, evenly mixing, obtains the aqueous gel shape polymer that about 73% (mole) of vinylformic acid is neutralized.This aqueous gel shape polymer surface temperature is 180 ℃ a rotary drum dryer drying, is ground into the following granularity of particle diameter 850 μ m, obtains water-absorbent besin particles (b11).(b11) contain the following particulate of 5.2% particle diameter, 105 μ m, also contain the following particulate of 0.8% particle diameter, 45 μ m.The results are shown in Table 2 in the performance measurement of this water-absorbent besin particles (b11).
Comparative example 12
In the 200ml flask, add 65.4g vinylformic acid, 78.6g deionized water, be cooled to 20～30 ℃, Dropwise 5 6.0g 48% aqueous sodium hydroxide solution that under agitation blows slowly simultaneously makes the vinylformic acid neutralization of 74% (mole).Dissolving 0.2g N in this monomer solution, N '-methylene diacrylamine adds the 0.1g Potassium Persulphate then, after the room temperature dissolving, feeds nitrogen, and the dissolved oxygen content in the solution is dropped to below the 1ppm.
In the 1L flask of reflux exchanger is housed, add the 400g normal hexane, behind the dissolving 3g sorbitan stearate, feed nitrogen, the dissolved oxygen content in the solution is dropped to below the 1ppm.Make temperature be maintained at about 60 ℃ with the temperature bath then, drip the monomer solution that contains above-mentioned Potassium Persulphate while stirring, carry out polymerization in about 3 hours, under refluxad continue polymerization 2 hours then, obtain pearl aqueous polymerization dispersion liquid.Filter out the aqueous polymerization body from this polymer dispersed liquid, further centrifuge dehydration obtains pearl aqueous polymerization body.This aqueous polymerization body obtains the bead-shaped water absorbing resin particle (b12) of the following granularity of particle diameter 850 μ m at 90～95 ℃ of drying under reduced pressure.(b12) contain the following particulate of 6.4% particle diameter, 105 μ m, and the following particulate of particle diameter 45 μ m accounts for 0.9%.The results are shown in Table 2 in the performance measurement of this water-absorbent besin particles (b12).
Embodiment 5
100 parts of water-absorbent besin particles (b8) and 0.05 part of dimethyl silicone oil " the シ リ コ of SHIN-ETSU HANTOTAI-Application KF96A-100 " [SHIN-ETSU HANTOTAI's chemical industry (strain) systems that comparative example 8 obtains; Surface tension 20.9 dyne/cm; Viscosity 100cps; Molecular-weight average about 6,000] add in the V-Mixer, mixed 20 minutes, obtain having and water-absorbent besin particles (b8) the modified water absorbent resin particle of the present invention (a5) of size-grade distribution equally almost.The results are shown in Table 2 in the performance measurement of this water-absorbent besin particles (a5).
Embodiment 6 and 7
Except that the addition of dimethyl silicone oil " the シ リ コ of SHIN-ETSU HANTOTAI-Application KF96A-100 " replaces with 0.01% and 0.1% respectively for water-absorbent besin particles (b8) among the embodiment 5, carry out similarly to Example 5, obtain modified water absorbent resin particle of the present invention (a6) and (a7).The results are shown in Table 2 for these water-absorbent besin particles (a6) and performance measurement (a7).
Embodiment 8～10
Remove dimethyl silicone oil " the シ リ コ of SHIN-ETSU HANTOTAI-Application KF96-50 " [surface tension 20.8 dyne/cm: viscosity 50cps that " the シ リ コ of SHIN-ETSU HANTOTAI-Application KF96A-100 " among the embodiment 5 uses SHIN-ETSU HANTOTAI's chemical industry (strain) to make respectively; Molecular-weight average about 3,500], dimethyl silicone oil " the シ リ コ of SHIN-ETSU HANTOTAI-Application KF96-350 " [surface tension 21.1 dyne/cm; Viscosity 350cps; Molecular-weight average about 15,000] and dimethyl silicone oil " the シ リ コ of SHIN-ETSU HANTOTAI-Application オ イ Le KF54 " [surface tension 25.2 dyne/cm; Viscosity 400cps; Molecular-weight average about 16,000] replace outside, carry out similarly to Example 5, obtain modified water absorbent resin particle of the present invention (a8), (a9) and (a10).The results are shown in Table 2 in the performance measurement of these water-absorbent besin particles.
Embodiment 11 and 12
Remove dimethyl silicone oil " the シ リ コ of SHIN-ETSU HANTOTAI-Application KF96-5 " (surface tension 19.7 dyne/cm that " the シ リ コ of SHIN-ETSU HANTOTAI-Application KF96-100 " among the embodiment 5 uses SHIN-ETSU HANTOTAI's chemical industry (strain) to make respectively; Viscosity 5cps; Molecular-weight average about 100), dimethyl silicone oil " the シ リ コ of SHIN-ETSU HANTOTAI-Application KF96-3000 " (surface tension 21.3 dyne/cm; Viscosity 3,000cps; Molecular-weight average about 40,000) replace outside, carry out similarly to Example 5, obtain modified water absorbent resin particle of the present invention (a11) and (a12).The results are shown in Table 2 in the performance measurement of these water-absorbent besin particles.
Embodiment 13
Add the silicon-dioxide (" レ オ ロ シ-Le Q S-102 " of 0.02% wetting ability degree 100% in the water-absorbent besin particles that embodiment 5 obtains (a5); Moral mountain Cao Da (strain) system), uniform mixing obtains modified water absorbent resin particle of the present invention (a13).The results are shown in Table 2 in the performance measurement of this water-absorbent besin particles (a13).
Embodiment 14～16
Water-absorbent besin particles in embodiment 5 (b8) use respectively absorbent resin (b9), (b10) and (b12) replace, carry out similarly to Example 5, obtain modified water absorbent resin particle of the present invention (a14), (a15) and (a16).The results are shown in Table 2 in the performance measurement of these water-absorbent besin particles.
Table 2
Water-absorbent besin particles Normal pressure absorbed dose (g/g) Pressurizing absorption amount (g/g) Absorption rate (second) Perviousness Ning Jiaoization Time Inter (second)
Comparative example 8 (b8) 56 21 88 × More than 500
Embodiment 5 (a5) 56 21 18 ◎ 42
Embodiment 6 (a6) 56 21 25 ◎ 78
Embodiment 7 (a7) 55 22 16 ◎ 64
Embodiment 8 (a8) 56 21 18 ◎ 51
Embodiment 9 (a9) 55 20 23 ◎ 76
Embodiment 10 (a10) 56 22 20 ◎ 52
Embodiment 11 (a11) 54 18 38 ○ 92
Embodiment 12 (a12) 52 16 41 ○ 98
Embodiment 13 (a13) 57 22 14 ◎ 38
Comparative example 9 (b9) 52 30 55 ○ 148
Embodiment 14 (a14) 52 31 8 ◎ 31
Comparative example 10 (b10) 56 21 82 △ 255
Comparative example 11 (b11) 58 22 93 × More than 500
Embodiment 15 (a15) 58 23 20 ◎ 41
Comparative example 12 (b12) 54 18 102 × More than 500
Embodiment 16 (a16) 55 19 30 ◎ 55
Can judge from table 2, modified water absorbent resin particle of the present invention and contain this grains of composition, compare with corresponding comparative example, normal pressure absorbed dose, the such performance of pressurizing absorption amount do not worsen, and absorption rate is faster, perviousness is excellent, gelation time has tremendous improvement.
The possibility of utilizing on the industry
Modified water absorbent resin particle of the present invention is as described below, has improved infiltration rate, has improved the moisture absorption caking capacity and has sent out dirt, also keeps or has improved the absorbent properties that water-absorbing resins has.
1) improves infiltration rate
1. not only to water, even being discharged liquid, the human bodies such as salting liquid, urine, blood also showing fast infiltration rate. Compare with the water-absorbent besin particles before processing with organopolysiloxane, infiltration rate improves about 1/2～1/4.
2. after wetting by uniform liquid on the water-absorbent besin particles surface, liquid just is penetrated into granule interior, thereby water absorbent gel occurs rapidly.
Even 3. water-absorbent besin particles contains the little particulate of a large amount of particle diameters, namely demonstrate fast infiltration rate.
2) improve moisture absorption caking capacity and a dirt
1. because the expeditiously set or be attached to the water-absorbent besin particles surface of the organopolysiloxane that has a water resisting property, thereby the moisture absorption caking rate is low. Therefore, even use in the environment of high humility, water-absorbing resins does not lump yet, thereby processing performance is excellent.
2. because organopolysiloxane is liquid, thus different from other method of adding hydrophobicity attritive powder etc., rely on the wetability effect to reduce the dust degree. Therefore, particulate can not occur yet disperse even dispose in a large number water-absorbent besin particles, improved operating environment, reduced the chance that operating personnel suck dust yet.
3. because the amount of dispersing is few, thereby reduce the loss late of water-absorbent besin particles in the paper nappy etc., improved productivity ratio.
3) maintenance or raising absorbent properties
1. after using the organopolysiloxane modification, also demonstrate with modification before identical or higher absorbent properties.
2. particularly use with modification before the situation of organopolysiloxane of responding property of water-absorbing resins under, owing to occur crosslinkedly at the near surface of water-absorbing resins, thereby add initial stage uptake and the absorbency depressed and all improve than the water-absorbent besin particles before processing. Therefore, be used in the situation of paper nappy etc., can tolerating the load of infant weight etc. and absorb rapidly a large amount of urines etc., the amount of returning of urine etc. is low, and the dry sensation on paper nappy surface is excellent, demonstrates dry and comfortable sensation.
Owing to reached above-mentioned effect, modified water absorbent resin particle of the present invention is particularly suitable for amenities or the absorbability laying materials such as paper nappy (children use paper nappy with paper nappy and adult), sanitary napkin, pad for incontinence, absorbent breast pad, operation subgaskets, pet shield.
Modified water absorbent resin particle of the present invention also can be used for using the various uses of particle-shape water-absorbing resin, i.e. the purposes that contacts with foodstuff such as Perserving materials, cold insulation material, dropping liquid absorbing material; The water content in oil remover; Drier; The water-loss reducer of plant or soil etc.; The coagulating agent of ヘ De ロ etc.; The dewfall preventing agent; The sealing material that civil construction is used or packaging material; The waterproof material of cable or fiber optic cable, artificial snow etc.

Claims (8)

1. the water-absorbent besin particles of modification, it is to be that the particle of a kind of so water-fast in fact absorbent resin of crosslinked polymer (A) of the unitary ethylenically unsaturated monomers of main structure is handled the modified water absorbent resin particle form with the silicone oil that is in a liquid state under the normal temperature (B) with vinylformic acid and/or acrylate, wherein:
1. (A) and (B) be and mix and/or the state of reaction,
2. the granule content of particle diameter 10～1,000 μ m accounts for more than 95% (weight) in the particle of (A),
3. weight ratio (A)/(B) is 100/ (0.001～5).
2. the described modified water absorbent resin particle of claim 1, wherein (B) is 10～20 25 ℃ viscosity, 000cst, surface tension is 18～30 dyne/cm.
3. the modified water absorbent resin particle described in the claim 1 or 2, wherein (B) be intramolecularly have at least one can with the functional group's of carboxylic acid group and/or carboxylate group reaction sex change silicone oil.
4. the modified water absorbent resin particle described in the claim 3, wherein (B) is amino sex change silicone oil or epoxy sex change silicone oil.
5. the modified water absorbent resin particle described in the claim 1 or 2, wherein the molecular-weight average of (B) is 1,000.
6. the modified water absorbent resin particle described in the claim 1 or 2, before wherein (A) handles with (B), when handling or after handling, have more than at least 2 and can near the particle surface of (A), carry out further crosslinking Treatment with the functional group's of carboxylic acid group and/or carboxylate group reaction linking agent (C) with intramolecularly with (B) with (B).
7. the modified water absorbent resin particle described in the claim 1 or 2 wherein further adds the silicon-dioxide fines (D) of 0.001～2% (weight) for (A).
8. the modified water absorbent resin particle described in the claim 1 or 2, it is in 40 ℃, moisture absorption caking rate under the relative humidity 80% is below 20%, and the dust degree and has adding of normal saline solution depressed the absorption characteristic of initial stage absorbed dose more than 20g/g below 10cpm.
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