CN106007476B - antibacterial air sand composition and preparation method thereof - Google Patents
antibacterial air sand composition and preparation method thereof Download PDFInfo
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- CN106007476B CN106007476B CN201610335212.4A CN201610335212A CN106007476B CN 106007476 B CN106007476 B CN 106007476B CN 201610335212 A CN201610335212 A CN 201610335212A CN 106007476 B CN106007476 B CN 106007476B
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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
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Abstract
The invention discloses a kind of antibacterial air sand composition and preparation method thereof, the antibacterial air sand composition includes：100 parts by weight of basic material；1~10 parts by weight of matrix resin；1~13 parts by weight of silicone oil；1~10 parts by weight of antiseptic；1~20 parts by weight of moisturizer；1~20 parts by weight of filler；The basic material is silica dioxide granule；The matrix resin is the resin at least containing one or more polar groups in carboxyl, hydroxyl, amino.Antibacterial air sand composition in the present invention has that feel is very fine and smooth, texture is soft, light specific gravity and tack-free, it is highly susceptible to being molded and cracking is not easy to after being molded, wettability is very good, bacteriostasis property is very good, antibacterial time length, can play long-acting bacteriostatic effect.
Description
Technical field
The invention belongs to Material Field, and in particular to a kind of Air sand itself with restraining and sterilizing bacteria is prepared with it
Method.
Background technology
Air sand is a kind of toy popular in recent years, and air is husky to have extremely soft texture, is rubbed in pressing
During by suck and discharge air allow sand toughen up with it is soft.Children by by the touch of air sand continuation and
Beat oneself haunting graphical three-dimensional three-dimensional, this is remarkably contributing to the imagination of exploitation child, strengthens child's perception energy
Power, the manipulative ability for cultivating child.The composition of air sand main composition is the extensive silica of distributed in nature -- i.e. silica,
Fish shellfish powder, moisturizer etc..
At present, material is common for normal children's sand, and the characteristic of only common sand, safety and sanitation cannot be guaranteed.And air is husky
It is not from natural sand, there is sand, clay, the characteristic of plasticine, safety and sanitation are nontoxic, and have soft sense of touch.
Secondly, normal children's sand needs to add certain moisture to produce viscosity in moulding process, and air sand has certain glue
Property, without water and plasticity.Again, normal children is husky not soluble in water or enters water and changes, hard with what is become long afterwards, and air is sandy
Ground is soft, not coarse.Water is dissolved in, is never hardened, can Reusability.In addition, the very viscous hand of normal children's sand, sticking mould, Yi Song
Dissipate, shaping is difficult.
Hence it is highly desirable to by the improvement of formula and preparation process, it is a with good hand touch, quality to develop
Gently, it is tack-free, it is highly susceptible to shaping and very good cracking, wettability, asepsis environment-protecting is not easy to after being molded, there is preferable resist
Bacterium effect, antibacterial time are longer, can preserve for a long time, and the antibacterial air of Reusability is husky, can be used for educating, plays, kneading model
Works, drawing etc..
The content of the invention
In order to solve the above-mentioned technical problem, first aspect present invention provides a kind of antibacterial air sand composition, including：
The basic material is silica dioxide granule；
The matrix resin is the resin at least containing one or more polar groups in carboxyl, hydroxyl, amino.
In a preferred embodiment, in the basic material, the volume average particle size of silica for 0.01~
5mm。
In a preferred embodiment, epoxy resin is further included in the basic material.
In a preferred embodiment, the matrix resin is selected from：Acrylic resin, methacrylic resin, hydroxyl
One or more of mixing in base acrylic resin, polyvinyl alcohol resin, polyethylenimine resins, melmac.
In a preferred embodiment, the silicone oil is modified silicon oil.
In a preferred embodiment, the modified silicon oil is selected from amino-modified silicone oil, Carboxyl Modified Polydimethylsiloxane, hydroxyl
One or more of mixing in base modified silicon oil, polyether modified silicon oil.
In a preferred embodiment, the antiseptic has below formula：
A-B-C-D-E；
Described A, C, E are the segment including hydrophobic grouping；A, C, E can be the same or different；B, D is antibacterial chain
Section, B, D can be the same or different.
In a preferred embodiment, the antiseptic has below formula：
A-B-C-D-E；
Described A, the E is maleic anhydride modified polypropylene；Described B, the D is selected from：Chitosan, season aminated chitosan, guanidine
Any one in base chitosan；The E is polysiloxanes.
In a preferred embodiment, the filler is selected from：Talcum, clay, magnesium silicate, alumina silicate, sodium metasilicate,
Potassium silicate, mica, calcium carbonate, wollastonite, feldspar, thermoplastic microsphere, diatomite, Tourmaline, pearl powder, oyster shell whiting, lightweight
One or more of combinations in calcium carbonate.
Another aspect provides a kind of preparation method of antibacterial air sand composition, the step is at least wrapped
Include：The step of uniformly mixing following S1 and S2；
S1：Basic material, matrix resin, silicone oil, filler are provided, is uniformly mixed, obtains mixture A；
S2：Moisturizer, antiseptic are provided, is uniformly mixed, obtains mixture B.
The above-mentioned of the application and other features, aspect and advantage is more readily understood with reference to described further below.
Embodiment
Participate in the election of the detailed description of the invention below for being preferable to carry out method and including embodiment this hair can be more easily understood
Bright content.Unless otherwise defined, all technologies used herein and scientific terminology have common with fields of the present invention
The normally understood identical implication of technical staff.When there is a conflict, the definition in this specification shall prevail.
As used herein term " by ... prepare " it is synonymous with "comprising".Term "comprising" used herein, " comprising ",
" having ", " containing " or its any other deformation, it is intended that cover including for non-exclusionism.For example, the combination comprising listed elements
Thing, step, method, product or device are not necessarily limited to those key elements, but can include not expressly listed other key elements or
Such a composition, step, method, product or the intrinsic key element of device.
Conjunction " Consists of " excludes any key element do not pointed out, step or component.If be used in claim, this
Phrase will make claim be closed, it is not included the material in addition to the material of those descriptions, but relative normal
Except rule impurity.When being rather than immediately following in the clause that phrase " Consists of " appears in claim main body after theme,
It is only limited to the key element described in the clause；Other key elements are not excluded outside the claim as a whole.
Equivalent, concentration or other values or parameter are excellent with scope, preferred scope or a series of upper limit preferred values and lower limit
During the Range Representation that choosing value limits, this, which is appreciated that, specifically discloses by any range limit or preferred value and any scope
All scopes that any pairing of lower limit or preferred value is formed, regardless of whether the scope separately discloses.For example, when open
During 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 " etc..When number range is described herein, unless otherwise stated, otherwise the scope is intended to include its end
Value and all integers and fraction within the range.
Singulative includes plural number and object is discussed, unless the context clearly dictates otherwise." optional " or it is " any
It is a kind of " refer to that the item that describes thereafter or event may or may not occur, and the description include situation that event occurs and
The situation that event does not occur.
Approximate term in specification and claims is used for modifying quantity, represents specific the present invention is not limited to this
Quantity, further includes the modified part of the acceptable change without cause related basic function close to the quantity.Phase
Answer, modify a numerical value with " about ", " about " etc., mean that the invention is not restricted to the exact numerical.It is approximate in some examples
Term likely corresponds to the precision of the instrument of measured value.In present specification and claims, scope limits can be with
Combine and/or exchange, these scopes include all subranges contained therebetween if not stated otherwise.
In addition, indefinite article " one kind " before key element of the present invention or component and "one" quantitative requirement to key element or component
(i.e. occurrence number) unrestriction.Therefore "one" or " one kind " should be read as including one or at least one, and odd number
The key element or component of form also include plural form, unless the obvious purport of the quantity refers to singulative.
" polymer " means by the polymerizable compound prepared by the monomer that polymerize identical or different type.Generic term
" polymer " includes term " homopolymer ", " copolymer ", " terpolymer " and " copolymer ".
" copolymer " means the polymer prepared by polymerizeing at least two different monomers.Generic term " copolymer " includes
(its is general with term " terpolymer " for term " copolymer " (its generally to refer to the polymer prepared by two kinds of different monomers)
To refer to the polymer prepared by three kinds of different monomers).It also includes the polymerization for planting monomer by polymerization four or more to manufacture
Thing." blend " means that two or more polymer mixes the polymerization to be formed by physics or chemical method jointly
Thing.
First aspect present invention provides a kind of antibacterial air sand composition, including：
The basic material is silica dioxide granule；
The matrix resin is the resin at least containing one or more polar groups in carboxyl, hydroxyl, amino.
Basic material：
In the present invention, the basic material is silica, and the silica is also known as silica, chemical formula SiO2,
In silica crystals, 4 valence electrons of silicon atom and 4 oxygen atoms form 4 covalent bonds, and silicon atom is located at positive tetrahedron
Center, 4 oxygen atoms are located on 4 apex angles of positive tetrahedron, and whole crystal is a huge molecule, SiO2Represent composition
Simplest formula does not indicate that single silicon dioxide molecules, is only to represent the ratio between atom number of silicon and oxygen in silica crystals.
In the present invention, substantial amounts of silanol group is there are on the surface of the silica, also referred to as silicone hydroxyl.These silicon
Hydroxyl can produce physics and chemical interaction with the matrix resin in the present invention, silicone oil, antiseptic, moisturizer etc., into
And the Air sand in the present invention is caused to have the advantages that moist, easily molded, antibacterial, viscosity are good and tack-free.
Silica dioxide granule in the present invention can become spherical form or irregular shape all can, preferably spherical structure.
In one embodiment, the volume average particle size of the silica is 0.01~5mm.
In a preferred embodiment, the volume average particle size of the silica is 0.5~3mm.
Term " volume average particle size " refers to the silica of irregular contour and the diameter of its volume same sphere.This hair
In bright, the volume average particle size of silica is using the laser particle analyzer of Japanese Shimadzu Corporation, model：SALD-7101 is tested
Arrive.
In a preferred embodiment, volume average particle size is that the silica of 3~5mm accounts in the basic material
The 50~70% of basic material gross weight；Volume average particle size be 1~3mm silica account for basic material gross weight 10~
30%.
Certainly heretofore described basic material is not limited to silica, every using silica as main component
Material, belong to technical scheme.
In a preferred embodiment, the basic material further includes the epoxy resin of 0.01~0.1 parts by weight.
In the present invention, the epoxy resin can be diglycidyl ether type epoxy resin, cycloaliphatic epoxy resin, aliphatic
One or more in epoxy resin, glycolylurea epoxide resin.
In the present invention, the epoxy resin can also be glycidyl ester type epoxy resin, glycidyl amine epoxy tree
One or more in fat, acid imide epoxy resin, phenol aldehyde type epoxy resin, polyurethane-type epoxy resin.
In the present invention, the epoxy resin is bisphenol A type epoxy resin, methyl epoxy resin, 2,3- epoxy resin -2,3-
Dihydro -1,4- naphthoquinones, double (7- oxabicyclos [4.1.0] 3- methyl in heptan) adipate esters, 1,2,5,6- diepoxy resins cyclooctane,
Ethyl (2S, 3S) -2,3- epoxy resin -3- methylpropanes acid esters, hexane -1,6- diglycidyl ether, diethylene glycol diglycidyl
One or more in glycerin ether, tripropyleneglycol diglycidyl ether, neopentylglycol diglycidyl ether.
In addition, the epoxy resin in the present invention can also be other epoxy resin compounds, such as Bisphenol F type ring can be enumerated
Oxygen tree fat, cresol novolak type epoxy resin, phenol novolak type epoxy, biphenyl type epoxy resin, stilbene type epoxy resin, quinhydrones
Type epoxy resin, naphthalene skeleton type epoxy resin, four phenolic group ethane type epoxy resin, DPP types epoxy resin, three oxybenzene methylmethane types
Epoxy resin, bicyclopentadiene phenol-type epoxy resin, the diglycidyl ether of bisphenol A epoxy ethane additive product, bisphenol-A epoxy third
The diglycidyl ether of alkane addition product, phenyl glycidyl ether, phenyl glycidyl ether etc. have the shrink of an epoxide group
Glycerin ether.
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, the epoxy resin can use any type preparation method known to those skilled in the art to prepare
Obtain.
In the present invention, the principle of the preparation method of the epoxy resin can be basically classified into two classes：(1) carbon-carbon double bond
It is oxidized to epoxy bond；(2) substrate reactions containing epoxy bond.
The present inventor is found surprisingly that addition and a small amount of epoxy resin into basic material can be to basic materials
Surface is pre-processed, and especially can be prevented from reuniting between the less silica dioxide granule of volume average particle size, this hair
A person of good sense guesses the possible reason is silica particles contain substantial amounts of silicone hydroxyl, the interaction between silicone hydroxyl, meeting
So that the less silica of particle diameter is reunited, the addition of epoxy resin can effectively obstruct the work of silica silicone hydroxyl
With, improve system dispersiveness, so as to play beneficial effects of the present invention.
Matrix resin：
In the present invention, the matrix resin is at least containing one or more polar groups in carboxyl, hydroxyl, amino
Resin.
In the present invention, the polar group can be located at the end of chain, may be alternatively located at side chain, be preferably located at side chain.
In the present invention, as the resin containing carboxyl, as long as the resin containing carboxyl in resin, then do not limit especially
It is fixed.As the resin containing carboxyl, for example, can compatibly use by least one kind of monomer in acrylic acid and methacrylic acid
The copolymer combined with ethene.Specifically, it can be ethene-methacrylic acid copolymer (EMAA), ethene-propylene
Acid copolymer (EAA) and comprising at least one kind of in these copolymers.
Resin containing carboxyl, synthetically prepared by the following method can also obtain：(1) glycidyl (methyl) is passed through
Acrylate or 3,4- epoxycyclohexyl-methyls (methyl) acrylate etc. have epoxy group and the compound of unsaturated double-bond
Or (methyl) propylene acid chloride etc., make the addition as side base (pendant) of ethene unsaturated group, and what is obtained contains carboxylic
The resin of base；(2) glycidyl (meth) acrylate or 3,4- epoxycyclohexyl-methyls (methyl) acrylate etc. are made
The copolymer of compound and the compound with unsaturated double-bond in addition with epoxy group and unsaturated double-bond, with
The unsaturated carboxylic acid of (methyl) acrylic acid etc. produces reaction, generated secondary hydroxyl and multi-anhydride is produced obtained from reacting
Resin containing carboxyl；Make the acid anhydrides with unsaturated double-bond of maleic anhydride etc. with addition with unsaturated double-bond
There is the copolymer of compound, 2- ethoxys (methyl) acrylate etc. the compound of hydroxyl and unsaturated double-bond to produce reaction
The obtained resin containing carboxylic acid；(3) multi-functional epoxy compound is produced reaction with unsaturated monocarboxylic, make what is generated
Hydroxyl produces with saturation or unsaturated multi-anhydride and reacts the obtained resin containing carboxyl；(4) polyvinyl alcohol derivative is made
Deng the polymer containing hydroxyl and saturation or unsaturated multi-anhydride reaction after, make generated carboxylic acid with having in a molecule
There are epoxy group and the compound of unsaturated double-bond to produce and react the obtained resin containing carboxyl；(5) multi-functional epoxyization is made
Compound, unsaturated monocarboxylic, in a molecule at least have 1 alcohol hydroxyl group and with beyond the alcohol hydroxyl group of epoxy reaction
The reaction product of compound of 1 reactive base produce that reaction is obtained to contain carboxylic with saturation or unsaturated multi-anhydride
The resin of base；(6) multifunctional oxetane compound and the unsaturation at least in a molecule with 2 oxetanes rings are made
Monocarboxylic acid produces reaction, makes primary OH and saturation or unsaturated multi-anhydride in obtained modified oxetane resin
Produce and react the obtained resin containing carboxyl；(7) polyfunctional epoxy resin is made with after unsaturated carboxylic acid generation reaction, making
Polybasic acid anhydride, which produces, reacts the obtained resin containing carboxylic acid further with having 1 oxirane ring and 1 in molecule
The compound of above ethene unsaturated group, which produces, reacts obtained resin containing carboxyl etc., though above-mentioned resin can be enumerated,
But it is not limited to these.
In a preferred embodiment, the resin containing carboxyl can be selected from acrylic resin, metering system
One or more of mixing in acid resin, hydroxy olefine acid resin.
In the present invention, as the resin containing hydroxyl, as long as the resin containing hydroxyl in resin, then do not limit especially
It is fixed.As the resin containing hydroxyl, for example, can be selected from：The partly-hydrolysed thing of polyvinyl alcohol, polyvinyl alcohol, polysaccharide resins etc..
In the present invention, as the resin containing amino, the amino can be primary amino radical or secondary amino group oligomer or
The main chain portion that polymer is formed.As oligomer or polymer containing amino, more specifically, polyallyl is preferably selected from
Amine, polydiene propyl group amine, m-xylene diamine-epichlorohydrin polycondensate, polyvinylamine, 3- dialkylamino propyl (first
Base) acrylamide copolymer, (methyl) acrylic acid 2- dialkylamino ethyls copolymer, polyvinylamine, melamine etc..
In the present invention, in addition to the resin more than, other resins can also be added.For example, do not damaging effect of the present invention
In the range of fruit, polyamide-based resin, polyimide resin, phenolic resin etc. can also be added.
In the present invention, the effect that matrix resin is added in basic material is that these matrix resins can be in basic material
Expect the surface of silica into one layer of very thin 3 D stereo cross linking membrane, this layer of very thin film can greatly improve basic material
The touch feeling of silica, touch feeling is finer and smoother, soft, increases the cohesive force of system.The also unexpected hair of the present inventor
Existing very thin 3 D stereo cross linking membrane can also play the role of immobilized antiseptic and moisturizer.The present inventor guesses that its is possible
The reason is that：Contain polar group, such as carboxyl, amino, hydroxyl etc. in these resins, and these groups can be with basic material
Expect that the silicone hydroxyl on the surface of silica forms intermolecular force, such as Hyarogen-bonding, thus, matrix resin can be in base
The surface of plinth material forms protective film, there is provided beneficial effects of the present invention.
Silicone oil：
Basic material in the present invention is silica, and after adding matrix resin, matrix resin can be in basic material dioxy
The surface of SiClx forms one layer of very thin 3 D stereo cross linking membrane, has greatly improved the touch feeling of basic material at this time, still
The situation that feel is deteriorated occurs in basic material after prolonged use, so the effect of silicone oil of the present invention is into one
The touch feeling of body higher baseline material is walked, increases the cohesive force of system so that the antibacterial Air sand in the present invention is more easy to moulding.
In the present invention, the silicone oil can be enumerated selected from as follows, and methyl polysiloxane, high polymer methylpolysiloxane, gather
Ethylene oxide methyl polysiloxane copolymer, polyoxypropylene methyl polysiloxane copolymer and poly- (ethylene oxide, oxypropylene)
The ether such as methyl polysiloxane copolymer modified polyorganosiloxane, stearic epoxide methyl polysiloxane, stearoxyl trimethyl silane, first
Base hydrogenated diene polysiloxanes, decamethylcyclopentasiloxane, octamethylcy-clotetrasiloxane, tetrahydro tetramethyl-ring tetrasiloxane,
The cyclic polysiloxanes such as octamethylpolysiloxane and dodecamethylcyclohexasiloxane；Methyl phenyl silicone, trimethyl silica
Amino modified polysiloxane, the silanols such as base silicic acid, aminoethylaminopropyl siloxanes dimethylsiloxane copolymer change
Property polysiloxanes, alkoxy-modified polysiloxanes, fatty acid modified polysiloxanes, fluorine richness polysiloxanes, epoxy-modified poly-
Siloxanes, alkoxy-modified polysiloxanes perfluoropolyether, polyvinyl acetate dimethyl polysiloxane and these mixture.
In a preferred embodiment, the silicone oil is modified silicon oil.
The modified silicon oil is selected from amino-modified silicone oil, Carboxyl Modified Polydimethylsiloxane, hydroxyl modification silicone oil, polyether modified silicon oil
In one or more of mixing.
In the present invention, the amino-modified silicone oil refers to that amino is grafted on methyl polysiloxane molecule.
The amino can be：2- amino-ethyls, 3- amino propyl aminos, N- cyclohexyl -3- aminopropyls or N-
(2- amino-ethyls) -3- aminopropyls etc..
Amino-modified silicone oil used can be the amino-modified silicone oil of single kind, or the amino of two or more species
The mixture of modified silicon oil.
In the present invention, the amino-modified silicone oil can be by Shin-Etsu Chemial Co., Ltd (Shin-
EtsuChemicalCo., Ltd.) manufacture the trade mark such as KF-8009A, KF-8009B, KF8009C.
In the present invention, the Carboxyl Modified Polydimethylsiloxane refers to that carboxyl is grafted on methyl polysiloxane molecule.
The carboxyl can be：The unsaturated carboxylic acids such as acrylic acid, methacrylic acid or maleic acid, fumaric acid,
The aliphatic such as itaconic acid, citraconic acid unsaturated dicarboxylic and its mono-methyl, mono ethyl ester, single n-propyl, single isopropyl ester, Dan Zhengding
It is ester, single isobutyl ester, monocyclic pentyl ester, single cyclohexyl, monocyclic heptyl ester, monocyclic monooctyl ester, monomethyl cyclohexyl, single isobornyl thiocyanoacetate, monocyclic
Amylene base ester, monocyclic hexene base ester, monocyclic heptene base ester, monocyclic octenylester, list (bicyclic pentadiene) ester；It can also be acid anhydride
Structure, can be used the carboxylic acid anhydride monomers such as maleic anhydride, citraconic anhydride.
Carboxyl Modified Polydimethylsiloxane used can be the Carboxyl Modified Polydimethylsiloxane of single kind, or the carboxyl of two or more species
The mixture of modified silicon oil.
In the present invention, the hydroxyl modification silicone oil refers to that hydroxyl is grafted on methyl polysiloxane molecule.
The hydroxyl can be：Alcohols material containing hydroxyl, for example, the alcohols thing such as methanol, ethanol, propyl alcohol, butanol
Matter；It can also be the glucide containing hydroxyl, for example, glucose,
As hydroxyl modification silicone oil, X22-160AS of SHIN-ETSU HANTOTAI's chemical industry manufacture etc. can be enumerated.
In the present invention, the polyether modified silicon oil refers to polyether grafting to methyl polysiloxane molecule.
In the present invention, the polyether modified silicon oil refers to contain polyalkylene oxide groups in the side chain of dimethyl polysiloxane
For example, the group of ethylene oxide and propylene oxide.
As polyether modified silicon oil, DowCorningToraySiliconeCo. can be purchased from, the L-7604 of Ltd. and come
From Shin-EtsuChemicalCo., the KF-353 of Ltd..
In a preferred embodiment, the modified silicon oil is Carboxyl Modified Polydimethylsiloxane, hydroxyl modification silicone oil, polyethers
The mixture of modified silicon oil.
In a preferred embodiment, the essential oil of 0.5~3 parts by weight can also be included in the silicone oil.
Essential oil is volatile aromatic oil, it can be synthesis or can be planted by distilling, squeezing or extract to derive from
Thing, and the smell or flavor of the plant usually derived from them.Useful essential oil can provide antiseptic activity.These essential oils
In some also serve as flavor enhancement.Useful essential oil includes but not limited to citral, thymol, menthol, gaultherolin (winter
Blue or green oil), cineole, carvacrol, camphor, anethole, carvol, eugenol, isoeugenol, limonene,
Osimen, Decanol, oil of Cymbopogon winterianus, α-salpineol, methyl acetate, geraniol acetate, methyleugenol, cineol,
Linalool, ethyl Linalool, safrole vanillic aldehyde, spearmint oil, peppermint oil, lemon oil, orange oil, sage oil, rosemary oil,
Cinnamon oil, pimiento tree oil, laurel, pine needle oil, geraniol, verbenone, fennel oil, oreodaphene, benzaldehyde, bergamot
Oil, semen armeniacae amarae, chlorothymol, cinnamic acid, citronella oil, caryophyllus oil, coal tar, eucalyptus oil, guaiacol, tropolone
Derivative such as hinokitiol, lavender oil, mustard oil, phenol, phenyl salicylate, pine tar, pinke needle oil, sassafras oil, wide leaf smoke clothing
Careless oil, storax, thyme linaloe oil, tolu balsam, turpentine oil, caryophyllus oil and combinations thereof.In an embodiment
In, the essential oil is selected from thymol, gaultherolin, cineole, menthol and combinations thereof.
Antiseptic：
In the present invention, used antiseptic can be synthetic antibacterial agents, or pure natural antibacterial agent.
In the present invention, used synthetic antibacterial agents have below formula：
A-B-C-D-E；
Described A, C, E are the segment including hydrophobic grouping；A, C, E can be the same or different；B, D is antibacterial chain
Section, B, D can be the same or different.
The heretofore described segment containing hydrophobic grouping can be preferably polyolefin either improved polyalkene or non-
Water miscible polysiloxanes.Certainly the segment of the hydrophobic grouping in the present invention is not limited thereto, every to play phase same-action effect
Fruit is fallen within protection scope of the present invention.
Polyolefin used in the present invention can be that olefin(e) compound autohemagglutination form, or the copolymerization of a variety of olefin(e) compounds and
Into, for example, it may be ethene and carbon number be at least one kind of or several olefin(e) compound copolymerization in 5~20 α-alkene and
It is made.
Specifically, in addition to ethene, the alpha-olefin that carbon number is 3~20 can enumerate propylene, 1- butylene, 2- fourths
Alkene, 1- amylenes, 3-methyl-1-butene, 1- hexenes, 4-methyl-1-pentene, 3- Methyl-1-pentenes, 3- ethyl -1- amylenes, 4,4-
Dimethyl -1- amylenes, 4- methyl isophthalic acids-hexene, 4,4- dimethyl -1- hexenes, 4- ethyl -1- hexenes, 3- ethyl -1- hexenes, 1-
The alkene such as octene, 1- decene, 1- dodecylenes, tetradecene, cetene, 1- vaccenic acids, 1- eicosylenes, can be with
Individually or Several combinations use above-mentioned single polymers or copolymer.
In the present invention, the weight average molecular weight of the polyolefin is 100000~100000000.
In the present invention, the weight average molecular weight of the polyolefin is to be based on gel permeation chromatography (hreinafter referred to as
“GPC”.) measure and carry out the value after polystyrene conversion.The determination condition of GPC uses the condition test of this area routine, example
Such as, can test to obtain by the way of following.
Column：Following columns are connected in series and are used.
" 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℃；Eluent：Tetrahydrofuran (THF)；Flow velocity：1.0mL/ point
Clock；Injection rate：100 μ L (tetrahydrofuran solution of sample solution concentration 4mg/mL)；Standard specimen：Use following monodisperse polystyrenes
Alkene, makes standard curve.
In the present invention, the improved polyalkene refers to that the intramolecular of above-mentioned polyolefin introduces carboxyl, acid anhydrides, amino, hydroxyl
Base, halogen isopolarity group, but ensuring that the polar group of introducing does not influence the water solubility of polyolefin.
In a preferred embodiment, described A, C, E are preferably improved polyalkene；More preferably carboxyl or
Anhydride modified polyolefin.
Heretofore described antibacterial segment can be chitosan, season aminated chitosan, guanidinated chitosan, hyperbranched shell
Any one or the combination of several of them in glycan.
In a preferred embodiment, the antiseptic has below formula：
A-B-C-D-E；
Described A, the E is maleic anhydride modified polypropylene；Described B, the D is selected from：Chitosan, season aminated chitosan, guanidine
Any one in base chitosan, hyperbranched chitosan；The C is polysiloxanes.
Term " maleic anhydride modified polypropylene " refers to maleic anhydride (MAH) graft modification polypropylene in this specification
(PP), the maleic anhydride modified polypropylene as raw material of the present invention is not particularly limited, and can be commercially available acquisition, can also pass through
Solwution method, supercritical CO2The method synthesis well-known to those skilled in the art such as solwution method, fusion method, radiation method and solid phase method
Obtain.Wherein, when solwution method carries out PP grafting MAH, the graft reaction time is grown, and grafting efficiency is low, it is necessary to consume a large amount of poisonous, easy
Solvent is fired, production cost is high, big to human injury, pollutes environment, takes up an area big, it is difficult to realize continuous operation.It is therefore preferable that adopt
Use fusion method.
For example, maleic anhydride modified polypropylene is prepared with fusion method：By styrene and initiator peroxidating diisopropyl
Benzene mixes, dissolving, is made into the styrene solution of initiator.By polypropylene and maleic anhydride mixing resulting mixture, by polypropylene with
The mixture input double screw extruder of maleic anhydride, after its melting, by the styrene solution of initiator in twin-screw extrusion
The different barrel section continuous meterings input of machine, carries out melting graft reaction, obtains maleic anhydride modified polypropylene.
In the maleic anhydride modified polypropylene, the grafting rate of maleic anhydride is 0.5%~8%；Preferably, maleic anhydride
Grafting rate be 1%~5%, it is further preferred that the grafting rate of maleic anhydride be 4.5%.
Maleic anhydride grafting ratio is tested using acid-base titration in embodiment and comparative example in the present invention.
The main process of acid-base titration：Weigh 0.5g polypropylene grafted maleic anhydrides to be dissolved in the hot dimethylbenzene of 50mL, treat
The NaOH- ethanol solutions that 10mL 0.1mol/L are added in backward system are completely dissolved, flows back 10 minutes, makes in maleic anhydride
Anhydride group is fully reacted with alkali, after add micro deionized water (50 μ l) or pyridine/DMF while hot into system, promote acid
Acid anhydride is hydrolyzed into carboxylic acid.3 drop phenolphthalein indicators are added at the same time, afterwards with hydrochloric acid/isopropanol titration to terminal.If HCl/ aqueous isopropanols
Concentration is C (mol/L), titrates M (g) sample, consumption volume V1(mL) solution, blank titration consumption V2(mL), grafting rate G is pressed
Formula calculates：
G=C (V2-V1) × 98/ (2 × M × 1000) × 100%
In formula 98 be maleic anhydride molecular weight.
Heretofore described maleic anhydride modified polypropylene can also be commercially available.
In the present invention, the weight average molecular weight of the polysiloxanes is 10000~1000000.
In a kind of preferred embodiment, the antiseptic has below formula：
A-B-C-D-E；
Described A, the E is maleic anhydride modified polypropylene；The B is guanidinated chitosan, and the D is hyperbranched
Chitosan；The C is polysiloxanes.
In the present invention, the guanidinated chitosan refers to introduce guanidine radicals in the intramolecular of chitosan.
" guanidine radicals " in the present invention is a kind of alkaline group, has following structural formula：
In the present invention, the commercially available acquisition of the guanidinated chitosan can also be by known to those skilled in the art
Method synthesize.In the present invention, the synthetic method of guanidinated chitosan is with reference to Application No.：CN201210209258.3
Patent document described in method synthesize to obtain；In the present invention, the preparation method of hyperbranched chitosan is with reference to patent authorization number：
CN 100577688C；In the present invention, season aminated chitosan the same document of preparation method：《Colloid and polymer》, volume 25 the 2nd
Phase.
In one embodiment, the weight average molecular weight of the chitosan is 50000~8000000.
In one embodiment, the weight average molecular weight of the chitosan is 100000~5000000.
In one embodiment, the weight average molecular weight of the polysiloxanes is 80000~8000000.
In the present invention, the synthetic method of five block copolymers of A-B-C-D-E can be known to those skilled in the art
Any type method synthesize to obtain.
In a preferred embodiment, it is described can be with the following method：
(1) maleic anhydride modified polypropylene is dissolved in solvent xylene, guanidinated chitosan is added after being completely dissolved,
Catalyst is added, is refluxed 2~6h of reaction；
(2) maleic anhydride modified polypropylene is dissolved in solvent xylene, hyperbranched chitosan is added after being completely dissolved,
Catalyst is added, is refluxed 2~5h of reaction；
(3) after the product obtained in step (1) is uniformly mixed with the product obtained in step (2), polysiloxanes is added,
Electromagnetic agitation reacts 4~10h in 60~100 DEG C of constant temperature oil baths, cools down, filtering, and obtained product is spare.
Using five block copolymers as antiseptic, A-B-C-D-E copolymers, in the copolymer of the present invention in the present invention
In, it is antibacterial segment to have two sections of B, D, and A, C, E are non-antibacterial segment, for the segment containing hydrophobic grouping.Human hair of the present invention
It is existing, extraordinary antibacterial effect can be played using the antiseptic of five block copolymers, and antibacterial effect is very lasting, will not go out
Now with the increase of service life, there is situation about declining in anti-microbial property, and the present inventor is also found surprisingly that, five block copolymers
Antiseptic can also play moisturizing, increase basic material performance of keeping humidity, with touch feeling so that the whole antibacterial sand of air touches
Touch it is more soft, the present inventor's conjecture the possible reason is, hyperbranched chitosan is due to that with unique spherical structure, can adsorb
More bacteriums for carrying negative electricity, the surface of bacterium forms one layer of film for hindering its nutriment absorbed, and then upsets cell
Normal physiological activity, so as to kill bacterium, and produces synergistic effect with guanidinated chitosan；On the other hand, five block copolymerization
Thing can also with the superficiality of basic material into very thin 3 D stereo protect membrane interaction, form larger crosslinking protection
Film, on the one hand can improve the performance of keeping humidity of antibacterial air sand, on the other hand can also improve the touch feeling of air sand, may be used also
Immobilized antiseptic, protects antiseptic, thus provides beneficial effects of the present invention.
Heretofore described natural antiseptic can be plant extraction liquid, and exemplary plant extraction liquid may be selected from：
Tree-of-heaven extracting solution, garden burnet extracting solution, Radix Astragali extractive solution, cones of Pinus koraiensis extracting solution, Cortex Magnoliae Officinalis extracting solution, Radix Isatidis extraction
Liquid, Siraitia grosvenorii extracting solution, tea extract, Sweet tea extracting solution, Guava Leaf extracting solution, extract solution of bamboo leaves, white paeony root extract, fish
Raw meat grass extracting solution, seven leaf courage extracting solutions, vine tea extracting solution, Flos Lonicerae extractive solution, chrysanthemum extract liquid, giant knotweed extracting solution, sarcandra
Extracting solution, licorice extract, sorrel root extracting solution, frutus cnidii fruit extracting solution, scutellariae,radix extracting solution, Broussonetia extract
Deng the extract in the present invention is not limited to these cited certainly.
Moisturizer：
Moisturizer is further included in heretofore described antibacterial air sand composition, moisturizer is used to improve basic material and base
The cohesive force of matter resin, so that the antibacterial air sand of the present invention is easier to moulding, and the husky holding of air after moulding is not done
Dry state.
The moisturizer can enumerate：Polyethylene glycol, polypropylene glycol, ethylene glycol, propane diols, butanediol, diethylene glycol,
Dipropylene glycol, triethylene glycol, tripropylene glycol, 1,2,6- hexanetriols, dihydroxyethylsulfide (Thiodiglycol), 1,3-BDO,
1,5-PD, glycerine etc..
From the point of view of the good result for suppressing to include liquid component volatilization, in these moisturizer, preferably using third
Triol.Two or more above-mentioned can be applied in combination as moisturizer.
In the present invention, it is 1~20 parts by weight for the weight of basic material to use moisturizer, if moisturizer
Usage amount is very few, does not have corresponding moistening effect, and usage amount is excessive, then is unfavorable for the husky shaping of air.
Filler：
Filler is further included in heretofore described antibacterial air sand composition, filler is used for the cohesive force for improving air sand,
Increase the bulkiness of air sand, improve the touch feeling and texture of air sand.
In the present invention, the filler is selected from：Talcum, clay, magnesium silicate, alumina silicate, sodium metasilicate, potassium silicate, mica, carbon
One kind in sour calcium, wollastonite, feldspar, thermoplastic microsphere, diatomite, Tourmaline, pearl powder, oyster shell whiting, precipitated calcium carbonate
Or several combination.
Other usually used fillers can also use, as long as they insignificantly change the function of remaining component in formula
All may be used.
In the present invention, it is 1~20 parts by weight for the weight of basic material to make filler.
Additive：
The component that can be added in usual cosmetics can also be mixed into the range of the effect of the present invention is not hindered.Specifically
Ground, can enumerate finish, chelating agent, surfactant, powder, amino acids, polyaminoacid and its salt, sugar alcohol and its epoxyalkane
It is addition product, lower alcohol, animal and plant extracts, nucleic acid, vitamin, enzyme, antiinflammatory, fungicide, preservative, antioxidant, ultraviolet
Light absorbers, antiperspirant, pigment, pigment, oxidation dye, organic and inorganic particle, pH adjusting agent, pearling agent, wetting agent etc..This
It is some examples, naturally it is also possible to mix the component beyond these.
In the present invention, the pigment can concrete example be：Yellow uitramarine, orange pigment, red pigment, blue pigment,
Violet pigment, black pigment etc..Yellow uitramarine be, for example, C.I. pigment yellows (pigment yellow) 74,93,95,109,110,
120th, 128,138,139,151,154,155,173,180,185,193 etc..Orange pigment is, for example, C.I. pigment oranges
(pigment orange) 34,36,43,61,63,71 etc..Red pigment be, for example, C.I. paratoneres (pigment red) 122,
202 etc..Blue pigment is, for example, C.I. alizarol saphirols (pigment blue) 15 etc..Violet pigment is, for example, C.I. pigment violets
(pigment violet) 19,23,33 etc..Black pigment is, for example, C.I. pigment blacks (pigment black) 7 etc..Certainly, originally
Pigment described in invention is not limited to these.
Another aspect provides a kind of preparation method of antibacterial air sand composition, the step is at least wrapped
Include：The step of including uniformly mixing following S1 and S2；
S1：Basic material, matrix resin, silicone oil, filler are provided, are uniformly mixed；
S2：Moisturizer, antiseptic are provided, are uniformly mixed.
The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiments are only used
In the invention will be further described, it is impossible to be interpreted as limiting the scope of the invention, professional and technical personnel in the field
Some the nonessential modifications and adaptations made according to the content of the invention described above, still fall within protection scope of the present invention.
In addition, if without other explanations, raw materials used to be all commercially available, the experimental raw of other not specified (NS)s is purchased from
Aladdin reagent (Shanghai) Co., Ltd., and formula ratio used represents basic material for 100 parts by weight when institute in the example below
The parts by weight used.
Basic material：
A1：The volume average particle size of silica accounts for always for 3~5mm (volume average particle size of silica includes 3mm)
The 70% of weight；The volume average particle size of silica accounts for always for 1~3mm (volume average particle size of silica includes 1mm)
The 20% of weight；The volume average particle size of silica accounts for the 10% of gross weight for 0.01~1mm；Above-mentioned silica dioxide granule mixes
After conjunction, the bisphenol A type epoxy resin of 0.01 parts by weight is added, is uniformly mixed spare.
A2：The volume average particle size of silica accounts for always for 3~5mm (volume average particle size of silica includes 3mm)
The 50% of weight；The volume average particle size of silica accounts for always for 1~3mm (volume average particle size of silica includes 1mm)
The 30% of weight；The volume average particle size of silica accounts for the 20% of gross weight for 0.01~1mm.
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, originate in Jinan Chang Hua resin Chemical Co., Ltd.；
B4:(Hydroxylated acrylic resin accounts for the 70% of gross mass for Hydroxylated acrylic resin, melmac；Melamine
Resin account for gross mass 30%), Hydroxylated acrylic resin originates in Guangzhou Ke Ning Chemical Industry Science Co., Ltd, melmac production
In Weifang Jinsui River 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 accounts for the 30% of gross mass for Carboxyl Modified Polydimethylsiloxane, hydroxyl modification silicone oil, polyether modified silicon oil；
Hydroxyl modification silicone oil accounts for the 50% of gross mass；Polyether modified silicon oil 20%), it is purchased from Shin-Etsu Chemial Co., Ltd.
Antiseptic:
D1:A-B-C-D-E；(A is：Polyvinyl chloride；The B is：Chitosan；The C is：It is maleic anhydride modified poly-
Ethene (grafting rate of maleic anhydride is 4%), the D is：Chitosan；The E is：Maleic anhydride modified polypropylene (maleic acid
4.5%) grafting rate of acid anhydride is
Preparation method：
(1) polyvinyl chloride of 10 parts by weight is dissolved in solvent xylene, after being completely dissolved, the shell for adding 5 parts by weight gathers
Sugar, after stirring evenly, add catalyst stannous chloride, add radical initiator, bipyridine ligand reaction temperature for 50~
150 degrees Celsius, stirring 6~24h of reaction, obtained product is spare；
(2) the maleic anhydride modified polypropylene of 20 parts by weight is dissolved in solvent xylene, after being completely dissolved, adds 6 weights
The chitosan of part is measured, after stirring evenly, catalyst stannous chloride is added, adds radical initiator, bipyridine ligand reaction
Temperature is 50~150 degrees Celsius, stirring 6~24h of reaction, and obtained product is spare；
(3) after the product obtained in step (1) is uniformly mixed with the product obtained in step (2), 8 parts by weight are added
Maleic anhydride modified polypropylene, adding catalyst stannous chloride, addition radical initiator, bipyridine ligand reaction temperature is
100~150 degrees Celsius, stirring 10~24h of reaction, is filtered, obtained product is spare.
D2:A-B-C-D-E；(A is：Polybutene；The B is：Hyperbranched chitosan；The C is：Polysiloxanes, institute
Stating D is：Hyperbranched chitosan；The E is：Maleic anhydride modified polypropylene (grafting rate of maleic anhydride is 4.5%)
The same D1 of specific preparation method；
Use the same patent authorization number of preparation method of hyperbranched chitosan：Method shown in CN 100577688C.
D3:A-B-C-D-E；(A is：Polyvinyl chloride；The B is：Chitosan；The C is：Polyethylene, the D are：
Hyperbranched chitosan；The E is：Maleic anhydride modified polypropylene (grafting rate of maleic anhydride 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.
Use the same patent authorization number of preparation method of hyperbranched chitosan：Method shown in CN 100577688C.
D4:A-B-C-D-E；(A is：Maleic anhydride modified polypropylene (grafting rate of maleic anhydride is 0.5%)；Institute
Stating B is：Season aminated chitosan；The C is：Polysiloxanes, the D are：Hyperbranched chitosan；The E is：It is maleic anhydride modified
Polypropylene (grafting rate of maleic anhydride is 8%)
D5:A-B-C-D-E；(A is：Maleic anhydride modified polypropylene (grafting rate of maleic anhydride is 4.5%)；Institute
Stating B is：Guanidinated chitosan；The C is：Polysiloxanes, the D are：Hyperbranched chitosan；The E is：It is maleic anhydride modified
Polypropylene (grafting rate of maleic anhydride is 4.5%)；
The preparation method of guanidinated chitosan：Synthetic method with guanidinated chitosan is with reference to Application No.：
CN201210209258.3。
The same D1 of preparation method of A-B-C-D-E.
Filler:
F1:Clay
F2:Diatomite
F3:Wollastonite
F4:Tourmaline
Embodiment 1~9 and comparative example 1~6：
The preparation method of antibacterial air sand composition, the step include：Each parts by weight are as shown in table 1,
S1：Basic material, matrix resin, silicone oil, the filler of respective volume average grain diameter are provided, are uniformly mixed, stirring is straight
Blended to basic material, matrix resin, silicone oil, filler, in order to accelerate experiment process, can be suitably heat, mixed
Compound A；
S2：Moisturizer, antiseptic are provided, is stirred, obtains mixture B；
S3：The mixture A obtained in S1 and S2 steps, mixture B are stirred evenly, obtain product.
Comparative example 1：Basic material is that the particle volume diameter of 100 parts by weight is the silica of 5mm.
Each material composition table of table 1
Performance evaluation：
1st, dry strength is tested
Sample in embodiment 1~9 and comparative example 1~6, takes 20g respectively, is tiled into the culture dish of 50mm, by it
It is put into the drier in 25 DEG C, after 3 days, checks drying regime, wherein, very drying is 1, drying is 2, semi-moist is
3rd, moistening is 4.
2nd, Anti-microbial Performance Tests
Anti-microbial property is tested using QB/T4371-2012 methods, and test result is as shown in table 2.
3rd, 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) overall merit is carried out to the husky progress appearance of antibacterial air and feel respectively, the results are shown in Table 2 for overall merit.
2 product characterization result of table
Data above can be seen that with without using matrix resin, silicone oil, antiseptic product compared with, of the invention is antibacterial
Air is husky to have that feel is very fine and smooth, texture is soft, light specific gravity and tack-free, is highly susceptible to being molded and is not easy to out after being molded
Split, wettability is very good, bacteriostasis property is very good, antibacterial time length, can play long-acting bacteriostatic effect.
Foregoing example is merely illustrative, some features of the feature for explaining the disclosure.Appended claim
It is intended to require the scope as wide as possible being contemplated that, and embodiments as presented herein is only according to all possible embodiment
Combination selection embodiment explanation.Therefore, the purpose of applicant is appended claim not by the explanation present invention
Feature exemplary selectional restriction.And the progress in science and technology will not formed due to the inaccuracy of language performance and not
The possible equivalent or son being presently considered are replaced, and these changes should also be interpreted by appended in the conceived case
Claim covers.
Claims (4)
1. a kind of antibacterial air sand composition, by weight, it is characterised in that it includes：
The basic material is silica dioxide granule；
The matrix resin is the resin at least containing one or more polar groups in carboxyl, hydroxyl, amino；
Epoxy resin is further included in the basic material；
The matrix resin is selected from：It is acrylic resin, methacrylic resin, Hydroxylated acrylic resin, polyvinyl alcohol resin, poly-
One or more of mixing in ethene polyimide resin, melmac；
The silicone oil is modified silicon oil；
The modified silicon oil is selected from：In amino-modified silicone oil, Carboxyl Modified Polydimethylsiloxane, hydroxyl modification silicone oil, polyether modified silicon oil
One or more of mixing；
The antiseptic has below formula：
A-B-C-D-E；
Described A, the E is maleic anhydride modified polypropylene；Described B, the D is selected from：It is chitosan, season aminated chitosan, guanidinated
Any one in chitosan, hyperbranched chitosan；The C is polysiloxanes.
2. antibacterial air sand composition as claimed in claim 1, it is characterised in that in the basic material, silica
Volume average particle size is 0.01~5mm.
3. antibacterial air sand composition as claimed in claim 1, it is characterised in that the filler is selected from：Talcum, clay,
Magnesium silicate, alumina silicate, sodium metasilicate, potassium silicate, mica, calcium carbonate, wollastonite, feldspar, thermoplastic microsphere, diatomite, Tuo Ma
One or more of combinations in beautiful jade, pearl powder, oyster shell whiting, precipitated calcium carbonate.
4. the preparation method of the antibacterial air sand composition described in claims 1 to 3 any one, it is characterised in that described
The preparation method of antibacterial air sand composition includes at least：The step of uniformly mixing following S1 and S2；
S1：Basic material, matrix resin, silicone oil, filler are provided, is uniformly mixed, obtains mixture A；
S2：Moisturizer, antiseptic are provided, is uniformly mixed, obtains mixture B.
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| 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 |
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| 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 |
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| 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 |
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