CN106007476A - Antibacterial air-breathable sand composition and preparation method thereof - Google Patents
Antibacterial air-breathable sand composition and preparation method thereof Download PDFInfo
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- CN106007476A CN106007476A CN201610335212.4A CN201610335212A CN106007476A CN 106007476 A CN106007476 A CN 106007476A CN 201610335212 A CN201610335212 A CN 201610335212A CN 106007476 A CN106007476 A CN 106007476A
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- Prior art keywords
- antibacterial
- resin
- chitosan
- antibacterial air
- basic material
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
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- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63H—TOYS, e.g. TOPS, DOLLS, HOOPS OR BUILDING BLOCKS
- A63H33/00—Other toys
Abstract
The invention discloses an antibacterial air-breathable sand composition and a preparation method thereof. The antibacterial air-breathable sand composition comprises, by weight, 100 parts of basic material, 1-10 parts of matrix resin, 1-13 parts of silicon oil, 1-10 parts of antibacterial agent, 1-20 parts of moisturizing agent, and 1-20 parts of filling. The basic material refers to silicon dioxide particles; the matrix resin refers to resin containing at least one or multiple polar groups of carboxyl, hydroxyl and amino. The antibacterial air-breathable sand composition is fine and smooth in touch, soft in texture, light in specific gravity, tack-free, easy to shape, not easy to crack after being shaped, high in wettability, good in antibacterial property and long in bacterium resistance time, and has long-effective bacteriostatic effect.
Description
Technical field
The invention belongs to Material Field, be specifically related to a kind of self there is the Air sand of bacteriostasis and sterilization function with it
Preparation method.
Background technology
Air sand is the most popular a kind of toy, and air sand has extremely soft texture, in pressing
Sand is allowed to toughen up with soft by suction and air-out during rubbing.Children are by holding air sand
Continuing the touch of property and beat oneself haunting graphical three-dimensional three-dimensional, this is remarkably contributing to develop thinking of child
As power, strengthen child's perception, the manipulative ability of cultivation child.The composition of air sand main composition is nature
The Silicon stone that boundary is widely distributed--i.e. silicon dioxide, fish shellfish powder, wetting agent etc..
At present, normal children's sand material is common, the characteristic of only common sand, safety and sanitation it cannot be guaranteed that.And
Air sand is not from, in natural sand, having the characteristic of sand, clay, plasticine, safety and sanitation, nontoxic nothing
Evil, and have soft sense of touch.Next, normal children's sand needs to add certain moisture in moulding process and produces
Raw viscosity, and air sand has certain viscosity, it is not necessary to water and plasticity.Again, normal children's sand is insoluble
In water or enter water and i.e. change, hard with become long afterwards, and the sandy ground of air is soft, the most coarse.It is dissolved in water, never
Hardening, can Reusability.Additionally, normal children's sand glues hands, sticking mould very much, the loosest, molding is difficult.
Hence it is highly desirable to by formula and the improvement of preparation technology, with develop a have good hand touch,
Quality is light, tack-free, be not easy to after being highly susceptible to molding and molding cracking, wettability the best, without poison ring
Protect, to have preferable antibacterial effect, antibacterial time longer, can preserve for a long time, the antibacterial air of Reusability
Sand, may be used for education, game, kneading model works, drawing etc..
Summary of the invention
In order to solve above-mentioned technical problem, first aspect present invention provides a kind of antibacterial air sand compositions, bag
Include:
Described basic material is silica dioxide granule；
Described matrix resin is the resin at least containing one or more polar groups in carboxyl, hydroxyl, amino.
In a preferred embodiment, in described basic material, the volume average particle size of silicon dioxide is
0.01～5mm.
In a preferred embodiment, described basic material also includes epoxy resin.
In a preferred embodiment, described matrix resin is selected from: acrylic resin, methacrylic acid tree
One in fat, Hydroxylated acrylic resin, polyvinyl alcohol resin, polyethylenimine resins, melmac or
Several mixing.
In a preferred embodiment, described silicone oil is modified silicon oil.
In a preferred embodiment, described modified silicon oil is selected from amino-modified silicone oil, carboxy-modified silicon
The mixing of one or more in oil, hydroxyl modification silicone oil, polyether modified silicon oil.
In a preferred embodiment, described antibacterial has a below formula:
A-B-C-D-E；
Described A, C, E are the segment including hydrophobic group；A, C, E can be the same or different；
B, D are antibacterial segment, and B, D can be the same or different.
In a preferred embodiment, described antibacterial has a below formula:
A-B-C-D-E；
Described A, E is maleic anhydride modified polypropylene；Described B, D are selected from: chitosan, season ammonia
Change in chitosan, guanidinated chitosan any one；Described E is polysiloxanes.
In a preferred embodiment, described filler is selected from: Talcum, clay, magnesium silicate, aluminium silicate,
Sodium silicate, potassium silicate, Muscovitum, calcium carbonate, wollastonite, Anhydrite, thermoplastic microsphere, kieselguhr, Tuo Ma
The combination of one or more in beautiful jade, Margarita powder, conch meal, precipitated calcium carbonate.
Another aspect provides the preparation method of a kind of antibacterial air sand compositions, described step is at least
Including: uniformly mix the step of following S1 and S2；
S1: basic material, matrix resin, silicone oil, filler, mix homogeneously are provided, obtain mixture A；
S2: wetting agent, antibacterial, mix homogeneously are provided, obtain mixture B.
It is more readily understood the above-mentioned of the application and other features, aspect and advantage with reference to described further below.
Detailed description of the invention
Participate in the election of the detailed description being preferable to carry out method of the invention below and the embodiment that includes can be more easily understood
Present disclosure.Unless otherwise defined, all technology used herein and scientific terminology has and the present invention
The identical implication that one skilled in the art are generally understood that.When there is contradiction, with in this specification
Definition is as the criterion.
Term as used herein " by ... preparation " and " comprising " synonym.Term used herein " comprises ",
" include ", " having ", " containing " or its other deformation any, it is intended that cover the including of non-exclusionism.
Such as, comprise the compositions of listed elements, step, method, goods or device and be not necessarily solely those key elements,
But other not expressly listed key element or this kind of compositions, step, method, goods or device institute can be included
Intrinsic key element.
Conjunction " Consists of " gets rid of any key element, step or component do not pointed out.If wanted for right
In asking, this phrase will make claim be closed so that it is does not comprise the material in addition to the material that those describe,
But except relative customary impurities.In phrase " Consists of " occurs in the clause of claim main body
When being rather than immediately following after theme, it is only limited to the key element described in this clause；Other key element is not arranged
In addition in the described claim as entirety.
Equivalent, concentration or other value or parameter with scope, preferred scope or a series of upper limit preferred value and
During the Range Representation that lower preferable values limits, this is appreciated that and specifically discloses by any range limit or excellent
All scopes that arbitrary pairing of choosing value and any range lower limit or preferred value is formed, regardless of whether whether this scope
Separately disclose.Such as, when disclosing scope " 1 to 5 ", described scope should be interpreted as including
Scope " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to 5 ", " 1 to 3 and 5 "
Deng.When numerical range is described in this article, unless otherwise indicated, otherwise this scope is intended to include its end value
All integers within the range and mark.
Singulative includes that plural number discusses object, unless the context clearly dictates otherwise." optional " or
Person's " any one " refers to that the item described thereafter or event may or may not occur, and this description includes
The situation that the situation of event generation and event do not occur.
Approximation term in specification and claims is used for modifying quantity, represents that the present invention is not limited to this
Particular number, also includes close to this quantity acceptable without causing repairing of the change of relevant basic function
Positive part.Accordingly, modify a numerical value with " about ", " about " etc., mean and the invention is not restricted to this
Exact numerical.In some example, approximation term likely corresponds to measure the precision of the instrument of numerical value.In this Shen
Please be in specification and claims, scope limits and can combine and/or exchange, if not stated otherwise this
A little scopes include all subranges contained therebetween.
Additionally, indefinite article " a kind of " before key element of the present invention or component and " one " are to key element or component
Quantitative requirement (i.e. occurrence number) unrestriction.Therefore " one " or " a kind of " should be read as including one
Or at least one, and the key element of singulative or component also include plural form, unless the obvious purport of described quantity
Refer to singulative.
" polymer " means the polymerizable compound prepared by the monomer by being polymerized identical or different type.General
Term " polymer " " comprise term " homopolymer ", " copolymer ", " terpolymer " and " copolymerization
Body ".
" copolymer " means the polymer prepared by polymerization at least two different monomers.Generic term " copolymerization
Body " include term " copolymer " (it is typically in order to refer to the polymer prepared by two kinds of different monomers) and term
" terpolymer " (it is typically in order to refer to the polymer prepared by three kinds of different monomers).It also comprises by poly-
The polymer closing four or more kinds of monomers and manufacture." blend " means that two or more polymer passes through
Physics or the method for chemistry jointly mix and the polymer that formed.
First aspect present invention provides a kind of antibacterial air sand compositions, including:
Described basic material is silica dioxide granule；
Described matrix resin is the resin at least containing one or more polar groups in carboxyl, hydroxyl, amino.
Basic material:
In the present invention, described basic material is silicon dioxide, and described silicon dioxide is also known as Silicon stone, chemical formula
SiO2, in silica crystals, 4 valency electron and 4 oxygen atoms of silicon atom form 4 covalent bonds, silicon
Atom is positioned at the center of positive tetrahedron, and 4 oxygen atoms are positioned on 4 drift angles of positive tetrahedron, and whole crystal is
One huge molecule, SiO2It is to represent that the simplest formula of composition does not indicates that single silicon dioxide molecules, is only to represent two
The ratio of the atom number of silicon and oxygen in silica crystal.
In the present invention, the surface of described silicon dioxide there are substantial amounts of silanol group, also referred to as silicone hydroxyl.
These silicone hydroxyl can with the matrix resin in the present invention, silicone oil, antibacterial, wetting agent etc. produce physics and
Chemical interaction, and then make the Air sand in the present invention have moist, easy-formation, antibacterial, viscosity
The advantage such as good and tack-free.
Silica dioxide granule in the present invention can become spherical form or irregularly shaped all can, preferably spherical knot
Structure.
In one embodiment, the volume average particle size of described silicon dioxide is 0.01～5mm.
In a preferred embodiment, the volume average particle size of described silicon dioxide is 0.5～3mm.
Term " volume average particle size " refers to the silicon dioxide of irregular contour and the diameter of its volume same sphere.
In the present invention, the volume average particle size of silicon dioxide uses the laser particle analyzer of Shimadzu Corporation of Japan, model:
SALD-7101 test obtains.
In a preferred embodiment, in described basic material, volume average particle size is the dioxy of 3～5mm
SiClx accounts for the 50～70% of basic material gross weight；Volume average particle size be 1～3mm silicon dioxide account for basis
The 10～30% of material gross weight.
The most heretofore described basic material is not limited to silicon dioxide, and every is main with silicon dioxide
The material of composition, belongs to technical scheme.
In a preferred embodiment, described basic material also includes the epoxy of 0.01～0.1 weight portion
Resin.
In the present invention, described epoxy resin can be diglycidyl ether type epoxy resin, cycloaliphatic epoxy resin,
One or more in aliphatic epoxy resin, glycolylurea epoxide resin.
In the present invention, described epoxy resin can also be glycidyl ester type epoxy resin, glycidic amine type ring
One or more in epoxy resins, imide ring epoxy resins, phenol aldehyde type epoxy resin, polyurethane-type epoxy resin.
In the present invention, described epoxy resin be bisphenol A type epoxy resin, methyl epoxy resin, 2,3-asphalt mixtures modified by epoxy resin
Fat-2,3-dihydro-1,4-naphthoquinone, double (7-oxabicyclo [4.1.0] 3-methyl in heptan) adipate ester, 1,2,5,6-bicyclo-oxygen tree
Alicyclic ring octane, ethyl (2S, 3S)-2,3-epoxy resin-3-methylpropane acid esters, hexane-1,6-diglycidyl ether,
In diethylene glycol diglycidyl glycerin ether, tripropyleneglycol diglycidyl ether, neopentylglycol diglycidyl ether one
Plant or multiple.
It addition, the epoxy resin in the present invention can also be other epoxy resin compounds, such as bis-phenol can be enumerated
F type epoxy resin, cresol novolak type epoxy resin, phenol novolak type epoxy, biphenyl type epoxy resin,
Stilbene type epoxy resin, hydroquinone type epoxy resin, naphthalene matrix type epoxy resin, four phenolic group ethane type epoxy resin,
DPP type epoxy resin, three hydroxyphenyl methane type epoxy resin, bicyclopentadiene phenol-type epoxy resin, bisphenol-A
The diglycidyl ether of ethylene oxide adduct, the diglycidyl ether of bisphenol A propylene oxide addition product, benzene
Base glycidyl ether, phenyl glycidyl ether etc. have the glycidyl ether of an epoxide group.
Furthermore it is also possible to enumerate the nuclear hydrogenation epoxy resin of the nuclear hydrogenation compound as these epoxy resin.
In the present invention, described epoxy resin can use any preparation method known to those skilled in the art
Prepare.
In the present invention, the principle of the preparation method of described epoxy resin can be basically classified into two classes: (1)
Carbon-carbon double bond is oxidized to epoxy bond；(2) substrate reactions containing epoxy bond.
The present inventor is found surprisingly that, adds and a small amount of epoxy resin in basic material, can be to basis material
The surface of material carries out pretreatment, is especially possible to prevent between the silica dioxide granule that volume average particle size is less to send out
Raw reunion, the present inventor guesses that possible reason is that silica particles contains substantial amounts of silicone hydroxyl, silicon hydroxyl
Interaction between base, the silicon dioxide that particle diameter can be made less reunites, and the addition of epoxy resin is permissible
The effective effect intercepting silicon dioxide silicone hydroxyl, improves system dispersibility, thus plays the useful of the present invention
Effect.
Matrix resin:
In the present invention, described matrix resin is at least to contain one or more polarity in carboxyl, hydroxyl, amino
The resin of group.
In the present invention, described polar group may be located at the end of chain, it is possible to is positioned at side chain, is preferably located at
Side chain.
In the present invention, as the resin containing carboxyl, as long as contain the resin of carboxyl in resin, then do not have
It is particularly limited to.As the resin containing carboxyl, for example, it is possible to compatibly use by acrylic acid and methacrylic acid
In at least one monomer and ethylene combine the copolymer obtained.Specifically, can be ethylene methyl propylene
Acid copolymer (EMAA), ethylene acrylic acid co polymer (EAA) and comprise in these copolymers at least 1
Kind.
Resin containing carboxyl, it is also possible to the most synthetically prepared obtain: (1) passes through glycidyl
(methyl) acrylate or 3,4-epoxycyclohexyl-methyl (methyl) acrylate etc. there is epoxy radicals with unsaturated
The compound of double bond or (methyl) acrylic acid chloride etc., make ethylene unsaturated group as side base (pendant)
Addition, and the resin containing carboxyl obtained；(2) glycidyl (methyl) acrylate or 3,4-epoxy are made
The compound with epoxy radicals and unsaturated double-bond of cyclohexyl methyl (methyl) acrylate etc. with in addition
The copolymer of the compound with unsaturated double-bond, produce reaction with the unsaturated carboxylic acid of (methyl) acrylic acid etc.,
The resin containing carboxyl making generated secondary hydroxyl produce reaction with multi-anhydride and to obtain；Make maleic anhydride etc.
The copolymer of the anhydride with unsaturated double-bond and the compound with unsaturated double-bond in addition, 2-
Obtained by the compound with hydroxyl and unsaturated double-bond of ethoxy (methyl) acrylate etc. produces reaction
Resin containing carboxylic acid；(3) make multi-functional epoxy compound produce reaction with unsaturated monocarboxylic, make to be generated
Hydroxyl produce the resin containing carboxyl obtained by reaction with saturated or unsaturated multi-anhydride；(4) poly-second is made
After the polymer containing hydroxyl of enol derivatives etc. reacts with saturated or unsaturated multi-anhydride, make to be generated
Carboxylic acid and a part in have the compound of epoxy radicals and unsaturated double-bond produce obtained by reaction containing carboxylic
The resin of base；(5) make multi-functional epoxy compound, unsaturated monocarboxylic, in a part, at least have 1
Individual alcohol hydroxyl group and raw with the reaction of compound of 1 reactive base beyond the alcohol hydroxyl group of epoxy reaction
The resin containing carboxyl obtained by becoming thing and saturated or unsaturated multi-anhydride to produce reaction；(6) a part is made
In at least there is the multifunctional oxetane compound of 2 oxetanes rings produce with unsaturated monocarboxylic
Reaction, makes the primary OH in obtained modified oxetane resin produce with saturated or unsaturated multi-anhydride
The resin containing carboxyl obtained by raw reaction；(7) polyfunctional epoxy resin is made to produce reaction with unsaturated carboxylic acid
Afterwards, the resin containing carboxylic acid making polybasic acid anhydride produce obtained by reacting has 1 with molecule further
The compound of individual oxirane ring and more than 1 ethylene unsaturated group produce obtained by reaction containing carboxyl
Resin etc., though above-mentioned resin can be enumerated, but be not limited to these.
In a preferred embodiment, the described resin containing carboxyl can be selected from acrylic resin, methyl
The mixing of one or more in acrylic resin, hydroxy olefine acid resin.
In the present invention, as the resin containing hydroxyl, as long as contain the resin of hydroxyl in resin, then do not have
It is particularly limited to.As the resin containing hydroxyl, for example, it is possible to be selected from: polyvinyl alcohol, polyvinyl alcohol part soap
Compound, polysaccharide resins etc..
In the present invention, as the resin containing amino, described amino can be the oligomeric of primary amino radical or secondary amino group
The main chain portion that thing or polymer are constituted.As the oligomer containing amino or polymer, more specifically, preferably
For selected from PAH, polydiene propyl group amine, m-xylene diamine-epichlorohydrin polycondensate, polyethylene
Base amine, 3-dialkylamino propyl (methyl) acrylamide copolymer, (methyl) acrylic acid 2-dialkyl amido second
Ester copolymer, polyvinylamine, tripolycyanamide etc..
In the present invention, in addition to above resin, it is also possible to add other resin.Such as, this is not being damaged
In the range of invention effect, it is also possible to add polyamide-based resin, polyimide resin, phenolic resin etc..
In the present invention, the effect adding matrix resin in basic material is, these matrix resins can be at base
One layer of very thin 3 D stereo cross linking membrane that the surface of plinth materials silicon dioxide becomes, this layer of very thin film can be significantly
Improving the touch feeling of basic material silicon dioxide, touch feeling is finer and smoother, soft, increases the bonding of system
Power.The present inventor is also found surprisingly that very thin 3 D stereo cross linking membrane may also operate as immobilized antibacterial and moisturizing
The effect of agent.The present inventor guesses that its possible reason is: all contain polar group, such as carboxylic in these resins
Base, amino, hydroxyl etc., and these groups all can be formed with the silicone hydroxyl on the surface of basic material silicon dioxide
Intermolecular force, such as Hyarogen-bonding, thus, matrix resin can be formed on the surface of basic material and protect
Cuticula, it is provided that beneficial effects of the present invention.
Silicone oil:
Basic material in the present invention is silicon dioxide, and after adding matrix resin, matrix resin can be at basic material
The surface of silicon dioxide forms one layer of very thin 3 D stereo cross linking membrane, has the most been greatly improved touching of basic material
Touch feel, but basic material there will be the situation that feel is deteriorated after a long time use, thus of the present invention
The effect of silicone oil be the touch feeling of further height basic material, increase the cohesive force of system so that this
Antibacterial Air sand in invention is more easy to moulding.
In the present invention, described silicone oil can be enumerated selected from as follows, methyl polysiloxane, the poly-silica of high polymeric MAO
Alkane, polyoxyethylene methyl polysiloxane copolymer, polyoxypropylene methyl polysiloxane copolymer and poly-(oxygen
Ethylene, oxypropylene) the ether modified polyorganosiloxane such as methyl polysiloxane copolymer, stearic epoxide methyl polysilicon oxygen
Alkane, stearoxyl trimethyl silane, hydrogenated methyl diene polysiloxanes, decamethylcyclopentasiloxane, prestox
Cyclotetrasiloxane, tetrahydro tetramethyl-ring tetrasiloxane, octamethylpolysiloxane and dodecamethylcyclohexasiloxane
Deng cyclic polysiloxanes；Methyl phenyl silicone, trimethylsiloxy group silicic acid, aminoethylaminopropyl silicon
Amino modified polysiloxane, silanol-modified polysiloxanes, the alkoxyls such as oxygen alkane dimethylsiloxane copolymer
Modified polyorganosiloxane, fatty acid modified polysiloxanes, fluorine richness polysiloxanes, epoxy-modified polysiloxanes,
Alkoxy-modified polysiloxanes PFPE, polyvinyl acetate dimethyl polysiloxane and these mixture.
In a preferred embodiment, described silicone oil is modified silicon oil.
Described modified silicon oil changes selected from amino-modified silicone oil, Carboxyl Modified Polydimethylsiloxane, hydroxyl modification silicone oil, polyethers
The mixing of one or more in property silicone oil.
In the present invention, described amino-modified silicone oil refers to that amino is grafted on methyl polysiloxane molecule.
Described amino may is that 2-amino-ethyl, 3-amino propyl amino, N-cyclohexyl-3-aminopropyl,
Or N-(2-amino-ethyl)-3-aminopropyl etc..
Amino-modified silicone oil used can be the amino-modified silicone oil of single kind, or two or more kind
The mixture of amino-modified silicone oil.
In the present invention, described amino-modified silicone oil can be by Shin-Etsu Chemial Co., Ltd
The trades mark such as KF-8009A, KF-8009B, KF8009C that (Shin-EtsuChemicalCo., Ltd.) manufactures.
In the present invention, described Carboxyl Modified Polydimethylsiloxane refers to that carboxyl is grafted on methyl polysiloxane molecule.
Described carboxyl may is that the unsaturated carboxylic acid such as acrylic acid, methacrylic acid, it is also possible to be maleic acid,
The aliphatic unsaturated dicarboxylics such as fumaric acid, itaconic acid, citraconic acid and mono-methyl thereof, mono ethyl ester, single n-propyl,
Single isopropyl ester, single N-butyl, single isobutyl ester, monocycle pentyl ester, single cyclohexyl, monocycle heptyl ester, monocycle monooctyl ester,
Monomethyl cyclohexyl, single isobornyl thiocyanoacetate, monocycle pentenyl ester, monocycle hexenyl ester, monocycle heptenyl ester, list
Cyclo-octene base ester, single (bicyclic pentadiene) ester；Can also is that acid anhydride structure, maleic anhydride, citraconic acid can be used
The carboxylic acid anhydride monomer such as acid anhydride.
Carboxyl Modified Polydimethylsiloxane used can be the Carboxyl Modified Polydimethylsiloxane of single kind, or two or more kind
The mixture of Carboxyl Modified Polydimethylsiloxane.
In the present invention, described hydroxyl modification silicone oil refers to that hydroxyl is grafted on methyl polysiloxane molecule.
Described hydroxyl may is that the alcohols material containing hydroxyl, such as, methanol, ethanol, propanol, butanol
Deng alcohols material；Can also is that the glucide containing hydroxyl, such as, glucose,
As hydroxyl modification silicone oil, the X22-160AS etc. that SHIN-ETSU HANTOTAI's chemical industry manufactures can be enumerated.
In the present invention, described polyether modified silicon oil refers to that polyether grafting is to methyl polysiloxane molecule.
In the present invention, described polyether modified silicon oil refers in the side chain of dimethyl polysiloxane containing polyoxyalkylene
Group such as, oxirane and the group of expoxy propane.
As polyether modified silicon oil, can be purchased from DowCorningToraySiliconeCo., Ltd. L-7604 and
KF-353 from Shin-EtsuChemicalCo., Ltd..
In a preferred embodiment, described modified silicon oil be Carboxyl Modified Polydimethylsiloxane, hydroxyl modification silicone oil,
The mixture of polyether modified silicon oil.
In a preferred embodiment, described silicone oil can also include the quintessence oil of 0.5～3 weight portions.
Quintessence oil is volatile aromatic oil, and it can be synthesis or can pass through distillation, squeeze or extract source
In plant, and it is generally of abnormal smells from the patient or the local flavor of the plant that they are derived from.Useful quintessence oil can provide anticorrosion
Activity.Some in these quintessence oils also serve as flavoring agent.Useful quintessence oil includes but not limited to citral, in hundred
Phenol, menthol, methyl salicylate (wintergreen oil), cineole, carvacrol, Camphora, anethole,
Carvone, acetaminol, isoeugenol, limonene, osimen, Decanol, oil of Cymbopogon winterianus, α-salpineol,
Methyl acetate, geraniol acetate, methyleugenol, eucalyptol, Linalool, ethyl Linalool, Cinnamomum porrectum (Roxb.) Kosterm.
Element vanillin, Oleum Menthae Rotundifoliae, Oleum menthae, Fructus Citri Limoniae oil, orange oil, sage oil, oil of rosemary, Oleum Cinnamomi,
Sweet green pepper tree oil, laurel, pine needle oil, geraniol, verbenone, Oleum Anisi Stellati, laurel fat, benzaldehyde,
Oleum bergamottae, Semen Armeniacae Amarum, chlorothymol, cinnamic aldehyde, citronella oil, Oleum Caryophylli, coal tar, Eucalyptus oil,
Guaiacol, Tropolone derivative such as hinokitiol, Oleum lavandula angustifolia, mustard oil, phenol, salicylic acid
Phenyl ester, Oleum Pini, pinke needle oil, Sassafras oil, oil of spike, styrax, thyme oil, Thomas balsam,
Oleum Terebinthinae, Oleum Caryophylli and combinations thereof.In one embodiment, described quintessence oil selected from thymol,
Methyl salicylate, cineole, menthol and combinations thereof.
Antibacterial:
In the present invention, the antibacterial used can be synthetic antibacterial agents, it is also possible to for pure natural antibacterial agent.
In the present invention, the synthetic antibacterial agents used has a below formula:
A-B-C-D-E；
Described A, C, E are the segment including hydrophobic group；A, C, E can be the same or different；
B, D are antibacterial segment, and B, D can be the same or different.
The heretofore described segment containing hydrophobic group can be preferably polyolefin or improved polyalkene or
The non-water-soluble polysiloxanes of person.Certainly the segment of the hydrophobic group in the present invention is not limited thereto, every
To identical action effect fall within protection scope of the present invention within.
Polyolefin used by the present invention can be that olefin(e) compound autohemagglutination forms, or multiple olefin(e) compound copolymerization
Form, for example, it may be at least one in the alhpa olefin that ethylene and carbon number are 5～20 or several alkene
Hydrocarbon compound copolymerization and prepare.
Specifically, in addition to ethylene, carbon number be 3～20 alpha-olefin can enumerate propylene, 1-fourth
Alkene, 2-butylene, 1-amylene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-Methyl-1-pentene,
3-ethyl-1-amylene, 4,4-dimethyl-1-amylene, 4-methyl isophthalic acid-hexene, 4,4-dimethyl-1-hexene, 4-
Ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecylene, tetradecene, 1-
The alkene such as hexadecene, 1-vaccenic acid, 1-eicosylene, can individually or Several combinations use above-mentioned list gather
Thing or copolymer.
In the present invention, described polyolefinic weight average molecular weight is 100000～100000000.
In the present invention, described polyolefinic weight average molecular weight be based on gel permeation chromatography (hreinafter referred to as
“GPC”.) measure and carry out the value after polystyrene conversion.The condition determination of GPC uses this area routine
Condition test, such as, can use following mode to test and obtain.
Post: following post is connected in series and uses.
" TSKgelG5000 " (7.8mmI.D. × 30cm) × 1 piece
" TSKgelG4000 " (7.8mmI.D. × 30cm) × 1 piece
" TSKgelG3000 " (7.8mmI.D. × 30cm) × 1 piece
" TSKgelG2000 " (7.8mmI.D. × 30cm) × 1 piece
Detector: RI (differential refractometer)；Column temperature: 40 DEG C；Eluent: oxolane (THF)；Flow velocity:
1.0mL/ minute；Injection rate: 100 μ L (tetrahydrofuran solution of sample solution concentration 4mg/mL)；Standard specimen:
Use following monodisperse polystyrene, make standard curve.
In the present invention, described improved polyalkene refers to that above-mentioned polyolefinic intramolecular introduces carboxyl, anhydride, ammonia
Base, hydroxyl, halogen isopolarity group, but ensure that the polar group of introducing does not affect polyolefinic water solublity.
In a preferred embodiment, described A, C, E are preferably improved polyalkene；Further preferably
For carboxyl or anhydride modified polyolefin.
Heretofore described antibacterial segment can be chitosan, season aminated chitosan, guanidinated chitosan, surpass
Any one or a few combination in branched chitosan.
In a preferred embodiment, described antibacterial has a below formula:
A-B-C-D-E；
Described A, E is maleic anhydride modified polypropylene；Described B, D are selected from: chitosan, season ammonia
Change in chitosan, guanidinated chitosan, hyperbranched chitosan any one；Described C is polysiloxanes.
In this specification, term " maleic anhydride modified polypropylene " refers to maleic anhydride (MAH) graft modification poly-third
Alkene (PP), the maleic anhydride modified polypropylene as raw material of the present invention is not particularly limited, and can be commercially available acquisition,
Solwution method, supercritical CO can also be passed through2This area skills such as solwution method, fusion method, radiation method and solid phase method
Method synthesis known to art personnel obtains.Wherein, when solwution method carries out PP grafting MAH, graft reaction
Time is long, and grafting efficiency is low, needs to consume the most poisonous, flammable solvent, and production cost is high, to human injury
Greatly, pollute environment, take up an area big, it is difficult to realize continuous operation.It is therefore preferable that employing fusion method.
Such as, maleic anhydride modified polypropylene is prepared with fusion method: by styrene and initiator peroxidating two
Isopropylbenzene mixes, and dissolves, is made into the styrene solution of initiator.Polypropylene and maleic anhydride are mixed into mixing
Thing, by the mixture input double screw extruder of polypropylene with maleic anhydride, after it is melted, by initiator
Styrene solution inputs at the different barrel section continuous meterings of double screw extruder, carries out melting graft reaction,
To maleic anhydride modified polypropylene.
In described maleic anhydride modified polypropylene, the percent grafting of maleic anhydride is 0.5%～8%；Preferably, horse
The percent grafting carrying out anhydride is 1%～5%, it is further preferred that the percent grafting of maleic anhydride is 4.5%.
In the present invention, in embodiment and comparative example, maleic anhydride grafting ratio uses acid-base titrations test.
The main process of acid-base titrations: weigh 0.5g polypropylene grafted maleic anhydride and be dissolved in the hot diformazan of 50mL
In benzene, in system, add the NaOH-ethanol solution of 10mL 0.1mol/L, backflow 10 until completely dissolved
Minute, make the anhydride group in maleic anhydride fully react with alkali, after add the deionized water (50 μ l) of trace while hot
Or pyridine/DMF is in system, promotes that anhydride is hydrolyzed into carboxylic acid.It is simultaneously introduced 3 phenolphthalein indicators, uses afterwards
Hydrochloric acid/isopropanol is titrated to terminal.If HCl/ aqueous isopropanol concentration is C (mol/L), titrate M (g) sample,
Consume volume V1(mL) solution, blank titration consumes V2(mL), percent grafting G is calculated as follows:
G=C (V2-V1) × 98/ (2 × M × 1000) × 100%
In formula, 98 is the molecular weight of maleic anhydride.
Heretofore described maleic anhydride modified polypropylene can also be commercially available.
In the present invention, the weight average molecular weight of described polysiloxanes is 10000～1000000.
In a kind of preferred embodiment, described antibacterial has a below formula:
A-B-C-D-E；
Described A, E is maleic anhydride modified polypropylene；Described B is guanidinated chitosan, described
D is hyperbranched chitosan；Described C is polysiloxanes.
In the present invention, described guanidinated chitosan refers to introduce guanidine radicals in the intramolecular of chitosan.
" guanidine radicals " in the present invention is the group of a kind of alkalescence, has a following structural formula:
In the present invention, the commercially available acquisition of described guanidinated chitosan, it is also possible to pass through those skilled in the art
Known method synthesis obtains.In the present invention, the synthetic method of guanidinated chitosan is with reference to Application No.:
Method synthesis described in the patent document of CN201210209258.3 obtains；In the present invention, hyperbranched shell gathers
The preparation method of sugar is with reference to license number: CN 100577688C；In the present invention, season aminated chitosan system
The same document of Preparation Method: " colloid and polymer ", the 2nd phase of volume 25.
In one embodiment, the weight average molecular weight of described chitosan is 50000～8000000.
In one embodiment, the weight average molecular weight of described chitosan is 100000～5000000.
In one embodiment, the weight average molecular weight of described polysiloxanes is 80000～8000000.
In the present invention, the synthetic method of described A-B-C-D-E five block copolymer, can be art technology
Any method synthesis known to personnel obtains.
In a preferred embodiment, described can adopt with the following method:
(1) maleic anhydride modified polypropylene is dissolved in solvent xylene, adds guanidinated after being completely dissolved
Chitosan, adds catalyst, return stirring reaction 2～6h；
(2) maleic anhydride modified polypropylene is dissolved in solvent xylene, adds hyperbranched after being completely dissolved
Chitosan, adds catalyst, return stirring reaction 2～5h；
(3), after the product obtained in step (1) uniformly being mixed with the product obtained in step (2), add
Entering polysiloxanes, in 60～100 DEG C of constant temperature oil baths, electromagnetic agitation reaction 4～10h, cooling, filter, obtain
Product is standby.
The present invention use five block copolymers as antibacterial, A-B-C-D-E copolymer, being total in the present invention
In polymers, having two sections of B, D to be antibacterial segment, A, C, E are non-antibacterial segment, for containing hydrophobic
The segment of group.The inventors discovered that, use the antibacterial of five block copolymers to play extraordinary antibacterial
Effect, and antibacterial effect is very lasting, does not haves the increase along with service life, declining occurs in anti-microbial property
Situation, the present inventor is also found surprisingly that, the antibacterial of five block copolymers may also operate as moisturizing, increase
Basic material performance of keeping humidity, with touch feeling so that the antibacterial sand of whole air touches more soft, the present inventor
Guess that possible reason is, hyperbranched chitosan due to have uniqueness spherical structure, it is possible to adsorb more with
The antibacterial of negative electricity, the surface of antibacterial defines one layer of film hindering its nutrient substance absorbed, and then upsets cell
Normal physiological activity, thus kill antibacterial, and produce synergism with guanidinated chitosan；On the other hand,
The very thin 3 D stereo protecting film that five block copolymers can also become with the superficiality of basic material interacts,
Form bigger crosslinking protecting film, on the one hand can improve the performance of keeping humidity that antibacterial air is husky, on the other hand also may be used
The touch feeling husky to improve air, also can immobilized antibacterial, protect antibacterial, thus provide the present invention's
Beneficial effect.
Heretofore described natural antibacterial can be plant extraction liquid, and exemplary plant extraction liquid is optional
From:
Ailanthus altissima (mill.) swingle extracting solution, Radix Sanguisorbae extracting solution, Radix Astragali extractive solution, cones of Pinus koraiensis extracting solution, Cortex Magnoliae Officinalis extracting solution, plate
Blue root extracting solution, Fructus Momordicae extracting solution, tea extract, Folium hydrangeae strigosae extracting solution, Folium Psidii Guajavae extracting solution, Folium Bambusae
Extracting solution, white paeony root extract, Herba Houttuyniae extract, Herba Gynostemmatis extracting solution, Ampelopsis grossedentata extracting solution, Flos Lonicerae are extracted
Liquid, chrysanthemum extract liquid, Rhizoma Polygoni Cuspidati extracting solution, Herba Pileae Scriptae extracting solution, Radix Glycyrrhizae extract, sorrel root extracting solution,
Fructus Cnidii fruit extracting solution, scutellariae,radix extracting solution, Broussonetia extract etc., the extract in certain present invention is not
It is limited to cited these.
Wetting agent:
Also including wetting agent in heretofore described antibacterial air sand compositions, wetting agent is used for improving basic material
With the cohesive force of matrix resin so that the antibacterial air sand of the present invention is easier to the sky after moulding, and moulding
Gas sand keeps moist state.
Described wetting agent can enumerate: Polyethylene Glycol, polypropylene glycol, ethylene glycol, propylene glycol, butanediol,
Diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1,2,6-hexanetriols, dihydroxyethylsulfide
(Thiodiglycol), 1,3 butylene glycol, 1,5-PD, glycerol etc..
From the point of view of suppression includes the good result that liquid component volatilizees, in these wetting agents, preferably make
Use glycerol.Above-mentioned two or more can be applied in combination as wetting agent.
In the present invention, used wetting agent is 1～20 weight portions for the weight of basic material, if protecting
The usage amount of humectant is very few, does not has corresponding moistening effect, and usage amount is too much, then be unfavorable for air sand molding.
Filler:
Also including filler in heretofore described antibacterial air sand compositions, filler is for improving the bonding that air is husky
Power, increases the bulkiness that air is husky, improves the husky touch feeling of air and texture.
In the present invention, described filler is selected from: Talcum, clay, magnesium silicate, aluminium silicate, sodium silicate, silicic acid
Potassium, Muscovitum, calcium carbonate, wollastonite, Anhydrite, thermoplastic microsphere, kieselguhr, tourmaline, Margarita powder,
The combination of one or more in conch meal, precipitated calcium carbonate.
Other normally used filler can also use, as long as they insignificantly change remaining component in formula
Function all may be used.
In the present invention, made filler is 1～20 weight portions for the weight of basic material.
Additive:
The composition that can add can also be mixed in usual cosmetics in the range of the effect not hindering the present invention.
Specifically, can enumerate oil preparation, chelating agen, surfactant, powder body, amino acids, polyamino acid and salt thereof,
Sugar alcohol and alkylene oxide adducts thereof, lower alcohol, animals and plants extract, nucleic acid, vitamin, enzyme, antiinflammatory,
Antibacterial, preservative, antioxidant, UV absorbent, antiperspirant, pigment, pigment, oxidation dye,
Organic and inorganic particle, pH adjusting agent, pearling agent, wetting agent etc..These are some examples, the most also may be used
To mix the composition beyond these.
In the present invention, described pigment can concrete example be: yellow uitramarine, orange pigment, red pigment, indigo plant
Color pigment, violet pigment, black pigment etc..Yellow uitramarine e.g. C.I. pigment yellow (pigment yellow) 74,
93、95、109、110、120、128、138、139、151、154、155、173、180、185、
193 etc..Orange pigment e.g. C.I. pigment orange (pigment orange) 34,36,43,61,63,71 etc..
Red pigment e.g. C.I. paratonere (pigment red) 122,202 etc..Blue pigment e.g. C.I. pigment
Blue (pigment blue) 15 etc..Violet pigment e.g. C.I. pigment violet (pigment violet) 19,23,33 etc..
Black pigment e.g. C.I. pigment black (pigment black) 7 etc..Certainly, heretofore described pigment is not
It is limited to these.
Another aspect provides the preparation method of a kind of antibacterial air sand compositions, described step is at least
Including: include the step uniformly mixing following S1 and S2；
S1: basic material, matrix resin, silicone oil, filler, mix homogeneously are provided；
S2: wetting agent, antibacterial, mix homogeneously are provided.
Below by embodiment, the present invention is specifically described.Be necessary it is pointed out here that, following example
It is served only for that the invention will be further described, it is impossible to be interpreted as limiting the scope of the invention, this field
Some nonessential improvement and adjustment that professional and technical personnel makes according to the content of the invention described above, still fall within this
The protection domain of invention.
It addition, illustrate without other, raw materials used is all commercially available, the experimental raw of other not specified (NS)s
It is purchased from Aladdin reagent (Shanghai) Co., Ltd., and in the example below, formula ratio used all represents that basic material is
The parts by weight used during 100 weight portion.
Basic material:
The volume average particle size of A1: silicon dioxide was 3～5mm (volume average particle size of silicon dioxide includes 3mm)
Account for the 70% of gross weight；The volume average particle size of silicon dioxide is 1～3mm (the volume average particle of silicon dioxide
Footpath includes 1mm) account for the 20% of gross weight；The volume average particle size of silicon dioxide is 0.01～1mm to account for gross weight
The 10% of amount；After the mixing of above-mentioned silica dioxide granule, add the bisphenol A type epoxy resin of 0.01 weight portion,
Mix homogeneously is standby.
The volume average particle size of A2: silicon dioxide was 3～5mm (volume average particle size of silicon dioxide includes 3mm)
Account for the 50% of gross weight；The volume average particle size of silicon dioxide is 1～3mm (the volume average particle of silicon dioxide
Footpath includes 1mm) account for the 30% of gross weight；The volume average particle size of silicon dioxide is 0.01～1mm to account for gross weight
The 20% of amount.
Matrix resin:
B1: acrylic resin, originates in three well groups；
B2: polyvinyl alcohol resin, originates in Jinan Chang Hua resin Chemical Co., Ltd.；
B3: polyethylenimine resins, originates in Jinan Chang Hua resin Chemical Co., Ltd.；
(Hydroxylated acrylic resin accounts for the 70% of gross mass for B4: Hydroxylated acrylic resin, melmac；Melamine
Polyimide resin accounts for the 30% of gross mass), Hydroxylated acrylic resin originates in Guangzhou Ke Ning Chemical Industry Science Co., Ltd, and three
Cymel originates in Jinsui River, Weifang source Chemical Co., Ltd..
Silicone oil:
C1: methyl polysiloxane, is purchased from Shin-Etsu Chemial Co., Ltd；
C2: amino-modified silicone oil, is purchased from Shin-Etsu Chemial Co., Ltd；
C3: Carboxyl Modified Polydimethylsiloxane, is purchased from Shin-Etsu Chemial Co., Ltd；
C4: hydroxyl modification silicone oil, is purchased from Shin-Etsu Chemial Co., Ltd；
C5: Carboxyl Modified Polydimethylsiloxane, hydroxyl modification silicone oil, (Carboxyl Modified Polydimethylsiloxane accounts for gross mass to polyether modified silicon oil
30%；Hydroxyl modification silicone oil accounts for the 50% of gross mass；Polyether modified silicon oil 20%), it is purchased from SHIN-ETSU HANTOTAI's chemical industry
Co., Ltd..
Antibacterial:
D1:A-B-C-D-E；(described A is: polrvinyl chloride；Described B is: chitosan；Described C is: Malaysia
Anhydride modified lldpe (percent grafting of maleic anhydride is 4%), described D is: chitosan；Described E is:
Maleic anhydride modified polypropylene (percent grafting of maleic anhydride is 4.5%)
Preparation method:
(1) polrvinyl chloride of 10 weight portions is dissolved in solvent xylene, after being completely dissolved, adds 5 weight portions
Chitosan, after stirring, adds catalyst Cu-lyt., adds radical initiator, bipyridine part
Reaction temperature is 50～150 degrees Celsius, and stirring reaction 6～24h, the product obtained is standby；
(2) the maleic anhydride modified polypropylene of 20 weight portions is dissolved in solvent xylene, after being completely dissolved, adds
The chitosan of 6 weight portions, after stirring, adds catalyst Cu-lyt., adds radical initiator, connection
Two pyridine ligand reaction temperatures are 50～150 degrees Celsius, and stirring reaction 6～24h, the product obtained is standby；
(3), after uniformly being mixed with the product obtained in step (2) by the product obtained in step (1), 8 are added
The maleic anhydride modified polypropylene of weight portion, adds catalyst Cu-lyt., adds radical initiator, di-
Pyridine ligand reaction temperature is 100～150 degrees Celsius, stirring reaction 10～24h, filters, the product obtained
Standby.
D2:A-B-C-D-E；(described A is: polybutene；Described B is: hyperbranched chitosan；Described C is:
Polysiloxanes, described D is: hyperbranched chitosan；Described E is: maleic anhydride modified polypropylene (Malaysia
The percent grafting of anhydride is 4.5%)
The concrete same D1 of preparation method；
Used the preparation method of hyperbranched chitosan with license number: the method shown in CN 100577688C.
D3:A-B-C-D-E；(described A is: polrvinyl chloride；Described B is: chitosan；Described C is: poly-second
Alkene, described D is: hyperbranched chitosan；Described E is: maleic anhydride modified polypropylene be (maleic anhydride
Percent grafting is 4.5%)
The same D1 of preparation method；
Season aminated chitosan the same document of preparation method: " colloid and polymer ", the 2nd phase of volume 25.
Used the preparation method of hyperbranched chitosan with license number: the method shown in CN 100577688C.
D4:A-B-C-D-E；(described A is: maleic anhydride modified polypropylene (percent grafting of maleic anhydride is 0.5%)；
Described B is: season aminated chitosan；Described C is: polysiloxanes, and described D is: hyperbranched chitosan；
Described E is: maleic anhydride modified polypropylene (percent grafting of maleic anhydride is 8%)
D5:A-B-C-D-E；(described A is: maleic anhydride modified polypropylene (percent grafting of maleic anhydride is 4.5%)；
Described B is: guanidinated chitosan；Described C is: polysiloxanes, and described D is: hyperbranched chitosan；
Described E is: maleic anhydride modified polypropylene (percent grafting of maleic anhydride is 4.5%)；
The preparation method of guanidinated chitosan: with the synthetic method reference Application No. of guanidinated chitosan:
CN201210209258.3。
The same D1 of preparation method of A-B-C-D-E.
Filler:
F1: clay
F2: kieselguhr
F3: wollastonite
F4: tourmaline
Embodiment 1～9 and comparative example 1～6:
The preparation method of antibacterial air sand compositions, described step includes: each weight portion is as shown in table 1,
S1: the offer basic material of respective volume mean diameter, matrix resin, silicone oil, filler, mix homogeneously,
Stirring is until basic material, matrix resin, silicone oil, filler blend, in order to accelerate experiment process, and can be suitable
Carrying out heat, obtain mixture A；
S2: wetting agent, antibacterial, stirring mixing are provided, obtain mixture B；
S3: the mixture A obtained in S1 and S2 step, mixture B are stirred, obtains product.
Comparative example 1: basic material is the silicon dioxide that the particle volume diameter of 100 weight portions is 5mm.
Table 1 each material composition table
Performance evaluation:
1, dry strength test
Embodiment 1～9 and comparative example 1～6 in sample, take 20g respectively, the cultivation of the 50mm that tiled to
In ware, put it in the exsiccator in 25 DEG C, after 3 days, check drying regime, wherein, very
To be dried be 1, to be dried be 2, semi-moist is 3, to moisten be 4.
2, Anti-microbial Performance Tests
Anti-microbial property uses the test of QB/T4371-2012 method, and test result is as shown in table 2.
3, overall merit
At 25 DEG C, select 100 people (wherein 3～10 years old for 50 people；11～20 years old for 30 people；21～
40 years old for 20 people) respectively antibacterial air sand is carried out outward appearance and feel carries out overall merit, overall merit
Result as shown in table 2.
Table 2 product characterization result
Data above it can be seen that compared with the product not using matrix resin, silicone oil, antibacterial, the present invention
Antibacterial air sand have that feel is the finest and the smoothest, texture is soft, light specific gravity and tack-free, be highly susceptible to molding,
And be not easy to after molding cracking, wettability is the best, bacteriostasis property is the best, the antibacterial time is long, can play
Long-acting bacteriostatic effect.
Aforesaid example is merely illustrative, for explaining some features of the feature of the disclosure.Appended right
Require to be intended to the widest scope that requirement it is contemplated that, and embodiments as presented herein is only according to all
The explanation of the embodiment of the selection of the combination of possible embodiment.Therefore, the purpose of applicant is appended power
Profit requires the selectional restriction of example inventive feature not being described.And progressive in science and technology will be formed by
The possible equivalent or the son that are not presently considered in the inaccurate reason of language performance are replaced, and these become
Change and also should be interpreted in the conceived case to be covered by appended claim.
Claims (10)
1. an antibacterial air sand compositions, by weight, it is characterised in that it includes:
Described basic material is silica dioxide granule；
Described matrix resin is the resin at least containing one or more polar groups in carboxyl, hydroxyl, amino.
Antibacterial air sand compositions the most as claimed in claim 1, it is characterised in that in described basic material,
The volume average particle size of silicon dioxide is 0.01～5mm.
Antibacterial air sand compositions the most as claimed in claim 1, it is characterised in that in described basic material
Also include epoxy resin.
Antibacterial air sand compositions the most as claimed in claim 1, it is characterised in that described matrix resin selects
From: acrylic resin, methacrylic resin, Hydroxylated acrylic resin, polyvinyl alcohol resin, polyvinylamine
The mixing of one or more in resin, melmac.
Antibacterial air sand compositions the most as claimed in claim 1, it is characterised in that described silicone oil is for changing
Property silicone oil.
Antibacterial air sand compositions the most as claimed in claim 1, it is characterised in that described modified silicon grease separation
From: the one or several in amino-modified silicone oil, Carboxyl Modified Polydimethylsiloxane, hydroxyl modification silicone oil, polyether modified silicon oil
The mixing planted.
Antibacterial air sand compositions the most as claimed in claim 1, it is characterised in that described antibacterial has
Below formula:
A-B-C-D-E；
Described A, C, E are the segment including hydrophobic group；A, C, E can be the same or different；
B, D are antibacterial segment, and B, D can be the same or different.
Antibacterial air sand compositions the most as claimed in claim 7, it is characterised in that described antibacterial has
Below formula:
A-B-C-D-E；
Described A, E is maleic anhydride modified polypropylene；Described B, D are selected from: chitosan, season ammonia
Change in chitosan, guanidinated chitosan, hyperbranched chitosan any one；Described E is polysiloxanes.
Antibacterial air sand compositions the most as claimed in claim 1, it is characterised in that described filler is selected from:
Talcum, clay, magnesium silicate, aluminium silicate, sodium silicate, potassium silicate, Muscovitum, calcium carbonate, wollastonite, Anhydrite,
One or more in thermoplastic microsphere, kieselguhr, tourmaline, Margarita powder, conch meal, precipitated calcium carbonate
Combination.
10. the preparation method of the antibacterial air sand compositions described in claim 1～9, it is characterised in that institute
State step at least to include: include uniformly mixing the step of following S1 and S2；
S1: basic material, matrix resin, silicone oil, filler, mix homogeneously are provided, obtain mixture A；
S2: wetting agent, antibacterial, mix homogeneously are provided, obtain mixture B.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106892592A (en) * | 2017-04-01 | 2017-06-27 | 青岛乐谷休闲游乐设备有限公司 | A kind of recreation ground shell is husky |
| CN108043047A (en) * | 2017-11-17 | 2018-05-18 | 河北金丰新材料科技有限公司 | Water for bathing colored suspended gel and preparation method thereof |
| CN108975775A (en) * | 2018-10-11 | 2018-12-11 | 靖向军 | A kind of novel children intelligence development cotton sand and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02198573A (en) * | 1989-01-27 | 1990-08-07 | Yoshiyuki Kikaku:Kk | Plastic toy |
| CN102311596A (en) * | 2010-07-02 | 2012-01-11 | 真彩文具有限公司 | Non-toxic and light resin clay composition and preparation method thereof |
| CN103011895A (en) * | 2012-12-03 | 2013-04-03 | 丽水卓越文具制造有限公司 | Air sand and preparation method thereof |
| CN104492096A (en) * | 2014-12-26 | 2015-04-08 | 浦江县金太郎玩具有限公司 | Temperature-changed toy space sand and preparation method thereof |
| CN104877455A (en) * | 2014-02-27 | 2015-09-02 | 真彩文具股份有限公司 | A low-viscosity antibacterial gel-ink thickening agent and a preparing method thereof |
-
2016
- 2016-05-19 CN CN201610335212.4A patent/CN106007476B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02198573A (en) * | 1989-01-27 | 1990-08-07 | Yoshiyuki Kikaku:Kk | Plastic toy |
| CN102311596A (en) * | 2010-07-02 | 2012-01-11 | 真彩文具有限公司 | Non-toxic and light resin clay composition and preparation method thereof |
| CN103011895A (en) * | 2012-12-03 | 2013-04-03 | 丽水卓越文具制造有限公司 | Air sand and preparation method thereof |
| CN104877455A (en) * | 2014-02-27 | 2015-09-02 | 真彩文具股份有限公司 | A low-viscosity antibacterial gel-ink thickening agent and a preparing method thereof |
| CN104492096A (en) * | 2014-12-26 | 2015-04-08 | 浦江县金太郎玩具有限公司 | Temperature-changed toy space sand and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106892592A (en) * | 2017-04-01 | 2017-06-27 | 青岛乐谷休闲游乐设备有限公司 | A kind of recreation ground shell is husky |
| CN106892592B (en) * | 2017-04-01 | 2019-06-28 | 青岛乐谷休闲游乐设备有限公司 | A kind of recreation ground shell is husky |
| CN108043047A (en) * | 2017-11-17 | 2018-05-18 | 河北金丰新材料科技有限公司 | Water for bathing colored suspended gel and preparation method thereof |
| CN108975775A (en) * | 2018-10-11 | 2018-12-11 | 靖向军 | A kind of novel children intelligence development cotton sand and preparation method thereof |
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| CN106007476B (en) | 2018-05-15 |
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